Nanoparticles and microparticles that improve the physical performance of formulations, preparations, and final products.

Abstract

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

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the priority and benefit of U.S. Provisional Patent Application No. 63 / 496,724, filed on April 18, 2023, the entire content of which is incorporated herein by reference for all purposes.

[0002] (Field of the Invention) The nanoparticles and microparticles of the present invention function as carriers for more effectively delivering nanomaterials to sealants, coatings, composites, adhesives, and other polymer products. Specifically, the present invention relates to matrix particles that carry 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 minimizing the amount of such nanomaterials. Optionally, cross - linking chemistry can be incorporated into the particles either simply on the surface or as ligands or oligomer - like structures that can even further enhance the stated physical performance. In one embodiment, the matrix particles described above are used as nanoparticle and / or microparticle carriers that are blended or mixed into a polymer or a reactive precursor mixture for further processing.

[0003] Generally speaking, in one embodiment, the present invention relates to matrix particles comprising a matrix material as defined below, a susceptor, and a releaseable component. In some embodiments, these particles have a core-shell structure, or are simply cores. The core is capable of changing its physical or chemical form, thereby enabling the release of the releaseable component. If the particle has a core-shell structure, one or more shells may be present. The susceptor may not be present in the shells, or may be present in one or more shells. Similarly, the releaseable component may be present in the shells, or may be present in one or more shells. Thus, the shells are physically or chemically modifiable materials, such as oligomers or polymer materials. The presence of a susceptor in the matrix particles is optional. Such matrix particles are mixed into a target physical or chemical composition that needs to be physically or chemically affected by applying an external force, such as high frequency or heat, which mixes with the matrix particles, modifies the matrix particles, and releases the releaseable component into the physical or chemical mixture or composition. [Background technology]

[0004] In composite material manufacturing, eliminating whole heating provides higher throughput and eliminates the need to cool equipment components or molding materials before removal from the mold. Currently, polymerization can be initiated by two-component mixing to achieve a complete reaction system by activating a catalyst with light or by whole heating the composition. Each has limitations by default. Whole heating is time-consuming, uses the maximum amount of energy and associated complex equipment, and results in performance limitations due to excess material through heating and cooling resulting from stress accumulated during polymerization. Whole heating cannot be used in adhesive applications using elastomer substrates with glass transition temperatures below room temperature. Two-component mixing can be the same or worse in complexity, each requiring complex mixing or metering equipment to achieve uniform curing and the appropriate mixing ratio. Light, by default, is limited to transparent objects, can only cure thinner objects, requires special packaging to block light, typically an excess catalyst amount of more than 1%, and typically an excess of thermal energy input, and also requires complex equipment. On the other hand, the active catalysts and co-catalysts embedded in the matrix particles improve the shelf life of the product. For example, in B-stage products such as thermosetting prepregs and film adhesives, the product is kept frozen until use to improve shelf life and usable time.

[0005] In industrial manufacturing or processing, it is desirable to avoid using overall heating, to use light to cure larger objects as required, to avoid using complex curing equipment, to eliminate the need for complex metal forming equipment, and to minimize the amount of catalyst packed and the two-component system or the limited pot life of a two-component system.

[0006] In bonding, overall heating limits the use of thicker substrates with higher glass transition temperatures. Higher molecular weight materials present challenges in accepting larger amounts of fillers or reinforcing materials such as crushed carbon fibers and glass fibers. The use of lower molecular weight materials would allow for the use of higher filler content. Uniform mixing of fillers and high performance without rheological problems would be advantages of using lower molecular weight materials.

[0007] Chemical activation through opaque objects is often limited as described above, unless the object is transparent enough to allow substantial light transmission. There is a particular need for techniques that can penetrate opaque materials over considerable distances. This would provide a new capability to initiate polymerization in objects filled with a variety of fillers to varying degrees, without the need for heat and, where possible, without limitations on light transmission.

[0008] With today's technological capabilities, the release of components in a chemical reaction must be triggered by the external environment of the chemical reaction chamber, rather than by events originating from within the particles. This is similar to bulk heating, or, if using external light, is limited by the thin dimensions.

[0009] Overall, there is a need to activate chemicals, eliminate overall heating, minimize energy use, minimize materials, and minimize catalyst use in order to achieve desired rapid chemistry, eliminate apparatus complexity, minimize its cost and space, minimize or eliminate invasive procedures, and achieve activation as required.

[0010] By incorporating nanomaterials into compositions, many desirable effects can be achieved, from subsequent realization to the final performance of the product. The functional materials described, and the effects of their formation, or covalent bonding, hydrogen, and van der Waals forces, can individually significantly increase toughness, elasticity, strength, wear resistance, product life, environmental resistance, and more.

[0011] Importantly, the addition of nanomaterials often involves both physical, chemical, and economic challenges.

[0012] In particular, nanomaterials such as graphene or other plate-like structures and / or nanotubes have properties that inherently lead to their physical association, which can result in aggregation, adhesion, and then network formation, all of which can limit harmful effects. Both van der Waals, which are chemical associations, and other associations, then ultimately lead to a dramatic increase in viscosity as the amount of the nanomaterial increases, for example, limiting the amount that can be added and thus limiting the range of desired effects that can be incorporated into a composition. Among them, carbon nanotubes are the nanomaterials most limited by these overall effects. This can, in particular, limit the overall amount of nanomaterial that can be incorporated, or the overall amount required to achieve a particular effect.

[0013] The latter effect can limit not only the amount of material that can be incorporated, but also the processing of the composition. For example, shear effects can limit pumping and mixing or blending, as the amount of energy required increases significantly, causing nanomaterials to wear down device components, accumulate heat, decompose compositional components, and / or initiate a variety of undesirable chemical and physical effects.

[0014] Economically, regardless of the extent to which the former is overcome, unnecessary and more expensive amounts of material may be incorporated to achieve the desired effect, often making many applications uneconomical and / or limiting overall economic use in the broadest market.

[0015] In summary, it would be useful to find more efficient and less restrictive methods for utilizing nanomaterials, particularly nanotubes and graphene, without the aforementioned limitations, or while significantly reducing them. [Overview of the Initiative] [Problems that the invention aims to solve]

[0016] In one embodiment, the present invention comprises a plurality of matrix particles including matrix particle A and / or matrix particle B, The matrix particle A comprises a core and, optionally, at least one shell. The core in question, (i) A matrix material which is capable of completely or partially altering its physical and / or chemical properties, (ii) at least one susceptor component, the at least one susceptor component being embedded in the matrix material, (iii) at least one releaseable component, the at least one releaseable component being embedded in the matrix material and capable of physically or chemically influencing a bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, The at least one shell, (iv) Optionally, the at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, (v) comprising at least one releaseable component, the at least one releaseable component embedded in the at least one shell, the at least one releaseable component capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, and The matrix particle B comprises a core and optionally at least one shell, and the core is (vi) A matrix material which is capable of completely or partially altering its physical and / or chemical properties, (vii) at least one releaseable component, the at least one releaseable component embedded in the matrix material, the at least one releaseable component capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, The at least one shell, (viii) Optionally, the at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, (ix) the at least one releaseable component, the at least one releaseable component being embedded in the at least one shell, and the at least one releaseable component being capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, The present invention relates to a plurality of matrix particles, wherein at least one susceptor component and / or emittable component can be activated through radio-frequency (RF), microwave (MW) radiation, thermal activation, mechanical polishing, or a combination thereof.

[0017] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the matrix material is derived from and / or comprises an organic material, a monomer material, an oligomer material, a polymer material, or a combination thereof.

[0018] In yet another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the at least one susceptor and / or the at least one releasable component is selected from the group consisting of fullerene compounds, 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 iron metals, oxides of one or more iron metals, SPIONs, one or more non-iron metals, oxides of one or more non-iron metals, transition metals, transition metal oxides, silicon carbide-based materials, boron nitride, and combinations of one or more thereof.

[0019] In one embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the dimensions of the at least one susceptor and / or the at least one releasable component range from about 0.1 nm to about 1000 μm, and optionally, the at least one susceptor and / or the at least one releasable component is functionalized and / or non-functionalized.

[0020] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the at least one susceptor and / or the at least one releasable component is within the at least one shell, and the at least one susceptor and the at least one releasable component are in direct or indirect contact.

[0021] In yet another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the matrix particles are partially or entirely coated with one or more layers of deformable material or force-improving material, and optionally, one or more of the layers contain the at least one susceptor and / or the at least one releasable component.

[0022] In one embodiment, the present invention relates to a plurality of matrix particles as described above, wherein at least one releaseable component is a single chemical substance, a combination of chemical substances, an organic chemical substance, and / or an inorganic chemical substance, and the at least one releaseable component comprises one or more catalysts, cocatalysts, coreactants, oxidizers, reaction inhibitors, accelerators, co-accelerators, fuels, explosives, or one or more combinations thereof.

[0023] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein at least one releaseable component is released when the matrix material or shell is subjected to deformation, dissolution, melting, expansion, contraction, rupture, plasticization, solvation, exposure to light, or a combination thereof.

[0024] In yet another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the particles are further chemically surface-modified through one or more chemical reactions, optionally comprising at least one releaseable component, and optionally subsequently forming a partial or complete coating.

[0025] In one embodiment, the present invention relates to a plurality of matrix particles having chemical functionality, wherein at least one releaseable component comprises a chemically functional monomer, the matrix material comprises a polymerization material, and optionally the matrix particles are coated with a polymerization coating.

[0026] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein one or more variable matrix materials comprise one or more of wax, polymethyl methacrylate (PMMA), styrene, or one or more polymers or copolymers thereof.

[0027] In yet another embodiment, the present invention relates to a process for preparing the plurality of matrix particles described above using processes A, B, C, D, or a combination thereof, (A) includes emulsification, dispersion, and / or suspension polymerization, or (B) includes core-shell polymerization, or (C) is a copolymerization, wherein the copolymerization step includes emulsification, dispersion, suspension polymerization, or a combination thereof. (D) is the following process: (i) A step of coating polymer microparticles with a material containing a susceptor and a releaseable component, (ii) A step of encapsulating microparticles containing a susceptor and releaseable components with a monomer material, oligomer material, or polymer material, and / or (iii) A step of fusing the susceptor and the releaseable component, (iv) A step of sealing the susceptor and releaseable components in external pores on the surface of a porous microsphere or internal pores within the core, This relates to a process that includes combinations of A, B, C, and D.

[0028] In one embodiment, the present invention relates to a process for influencing a chemical reaction, or a process for releasing at least one releaseable component from a plurality of matrix particles, (i) To provide a bulk reaction mixture, (ii) To provide the matrix particles described above, (iii) Incorporating the plurality of matrix particles into the bulk reaction mixture, (iv) optionally, incorporate the plurality of matrix particles into the bulk reaction mixture and thermally activate the susceptor components embedded in the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once. The bulk reaction mixture containing the plurality of matrix particles is heated, The present invention relates to a process that includes mechanically polishing the bulk reaction mixture containing the plurality of matrix particles, or a combination thereof.

[0029] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein CNTs are incorporated into the matrix particles by the method described above.

[0030] In yet another embodiment, the present invention relates to an article comprising the plurality of matrix particles described above.

[0031] In one embodiment, the present invention relates to the prepared article described above, wherein the whole or a part of it is (i) A polymerizable composition of at least one chemical substance or several polymerizable compositions, (ii) reinforced composite articles; (iii) Laminated articles, (iv) rigid laminated articles, (v) flexible laminate article; (vi) foam, or (vii) A combination of those, relating to articles.

[0032] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the composition is all or part of an adhesive, sealant, coating, paint, ink, plastic, molded plastic, thermosetting plastic, molded thermosetting plastic, or other polymer-forming composition.

[0033] In yet another embodiment, the present invention relates to a plurality of matrix particles described above, wherein the releaseable component is a catalyst selected from the group consisting of transition metal complexes; transition metal alkoxides; stannous(II) bis(2-ethylhexanoate); carboxylates, alkoxides, and stannous, bismuth, zinc, and titanium complexes; blockized superacids; dodecylbenzenesulfonic acid; dinonylnaphthalenesulfonic acid; N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine; organic bases; 1,8-diazabicyclo[5.4.0]undeca-7-ene; 1,5-diazabicyclo[4.3.0]nonene-5); (1,4-diazabicyclo2.2.2-octane); and combinations thereof.

[0034] In one embodiment, the present invention relates to a multilayer polymer composition comprising a first plurality of matrix particles described above, and one or more additional plurality of matrix particles described above, arranged on the first matrix particles to form one or more matrix particle layers.

[0035] In another embodiment, the present invention relates to a precursor, intermediate, or final monomer, oligomer, or polymer composition comprising a plurality of matrix particles as described above, wherein the composition is prepared by solid-phase polymerization or from a reactive hot-melt formulation.

[0036] In yet another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the plurality of matrix particles contain carbon nanotubes, and the carbon nanotubes are coated on and / or contained within the matrix particles.

[0037] In one embodiment, the present invention relates to a plurality of matrix particles as described above, wherein CNTs are incorporated into the plurality of matrix particles by a fusion process.

[0038] In another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the matrix particles are further coated with a functional nanoparticle emulsion.

[0039] In yet another embodiment, the present invention relates to a plurality of matrix particles as described above, wherein the matrix particles are further coated with a monofunctional reactive material or a bifunctional reactive material.

[0040] In one embodiment, the present invention relates to a precursor, intermediate, or final monomer, oligomer, or polymer composition comprising a plurality of matrix particles as described in any one of the above claims, wherein optionally the composition is prepared from a functionalized polymer formulation, and optionally the composition is prepared as a reactive blend with a non-reactive polymer or oligomer.

[0041] In another embodiment, the present invention is a process for influencing a chemical reaction, (i) To provide a bulk reaction mixture, (ii) To provide the plurality of matrix particles described above, (ii) Incorporating the plurality of matrix particles into the bulk reaction mixture, and bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once to thermally activate the susceptor components embedded in the matrix particles, The bulk reaction mixture containing the plurality of matrix particles is heated, This includes mechanically polishing the bulk reaction mixture containing the plurality of matrix particles, or a combination thereof. The bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for solid-phase polymerization. The bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive hot melt formulation. The bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive blend with a non-reactive polymer or oligomer, or The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a functionalized polymer formulation.

[0042] In yet another embodiment, the present invention relates to a process for increasing the overall filling amount of CNTs in a bulk physically or chemically variable composition by the process described above.

[0043] In one embodiment, the present invention relates to a process for maintaining lower viscosity when adding at least one additive to a bulk physically or chemically variable composition, the process comprising: incorporating the at least one additive as at least one releaseable component into a plurality of matrix particles as described above; and incorporating the plurality of matrix particles into a bulk physically or chemically variable composition.

[0044] In another embodiment, the present invention relates to a process for increasing the overall filling amount of additives in a bulk physically or chemically modifiable composition, (i) To provide a composition of the bulk that can be physically or chemically altered, (ii) Incorporating at least one additive as a releaseable component into the plurality of matrix particles described above, (ii) Incorporating multiple matrix particles into a bulk physically or chemically variable composition, and thermally activating susceptor components embedded within the matrix particles by bombarding the bulk physically or chemically variable composition with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once. A bulk physically or chemically modifiable composition containing multiple matrix particles is heated, This includes mechanically polishing a bulk physically or chemically modifiable composition containing multiple matrix particles, or a combination thereof. The present invention relates to a process in which, optionally, a bulk physically or chemically modifiable composition is a monomer composition, oligomer composition, or polymer composition, or a combination thereof, that is a precursor or intermediate for reactive hot-melt formulations, adhesives, coatings, or composites.

[0045] In yet another embodiment, the present invention relates to a process for maintaining lower viscosity when adding at least one additive to a bulk physically or chemically modifiable composition, (i) A step of providing a physically or chemically modifiable composition of the bulk, (ii) A step of incorporating the at least one additive as a releaseable component into the plurality of matrix particles described above. (ii) Incorporating the plurality of matrix particles into the bulk physically or chemically variable composition, and thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk physically or chemically variable composition with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once. The bulk, physically or chemically modifiable composition containing the plurality of matrix particles is heated, The process includes mechanically polishing the bulk, which is physically or chemically modifiable, containing the plurality of matrix particles, or a combination thereof. The present invention relates to a process in which, optionally, a bulk physically or chemically modifiable composition is a monomer composition, oligomer composition, or polymer composition, or a combination thereof, that is a precursor or intermediate for reactive hot-melt formulations, adhesives, coatings, or composites.

[0046] In another embodiment, the present invention relates to the plurality of matrix particles described above, wherein the releaseable component is a catalyst for curing, polymerizing, and reacting acrylates, silane-terminated polymers, hydrolysis, condensation catalysts, isocyanate trimerization, 1K moisture-curable isocyanates, melamine crosslinking systems, 2K polyurethanes, 1K blocked isocyanate-based polyurethanes, epoxy, esterification, and transesterification.

[0047] In one embodiment, the present invention is a matrix particle, (i) A matrix material, wherein the matrix is ​​capable of completely or partially altering its physical properties, (ii) at least one susceptor component, the at least one susceptor component being embedded in the matrix material, and the at least one susceptor component being thermally activated by electron radiation, (iii) relating to a matrix particle comprising at least one releaseable and / or activateable component embedded in the matrix and in close proximity to the susceptor component, wherein the at least one releaseable and / or activateable component is capable of influencing a chemical reaction.

[0048] In another embodiment, the present invention relates to the matrix particles described above, comprising one or more matrices conforming to discrete zones, wherein the discrete zones are one or more shapes, the discrete zones comprise a coating or diverse layers, each zone comprises about zero to several susceptors and / or releaseable components, and the matrix particles, in aggregates, comprise at least one zone containing susceptors and at least one zone containing releaseable components.

[0049] In yet another embodiment, the present invention relates to matrix particles as described above, wherein the matrix is ​​derived from and / or contains organic materials, inorganic materials, monomer materials, oligomer materials, polymer materials, or combinations thereof.

[0050] In another embodiment, the present invention relates to the matrix particles described above, wherein at least one susceptor is selected from the group consisting of fullerene compounds, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon nanotubes, doped carbon nanotubes, carbon sheets, one or more ferrous metals, one or more oxides of ferrous metals, superparamagnetic iron oxide (SPION), one or more nonferrous metals, one or more oxides of nonferrous metals, transition metals, transition metal oxides, silicon carbide-based materials, boron nitride, and one or more combinations thereof.

[0051] In yet another embodiment, the present invention relates to the matrix particles described above, wherein the dimensions of the susceptor are in the range of about 0.1 nm to about 1000 μm.

[0052] In one embodiment, the present invention relates to the matrix particles described above, wherein the susceptor comprises a functionalized susceptor, a non-functionalized susceptor, or both a functionalized susceptor and a non-functionalized susceptor.

[0053] In another embodiment, the present invention relates to the matrix particles described above, wherein the susceptor is in direct or indirect contact with the susceptor, and the matrix particles are located at the geometric center of the matrix material.

[0054] In yet another embodiment, the present invention relates to the matrix particles described above, wherein the susceptor and / or releaseable component is located on the outer layer of the matrix particle, and the susceptor and the releaseable component are in direct or indirect contact.

[0055] In one embodiment, the present invention relates to the matrix particles described above, wherein the matrix particles are partially or entirely coated on one or more layers of a deformable material.

[0056] In another embodiment, the present invention relates to the matrix particles described above, wherein the matrix particles are partially or entirely coated on one or more layers of a deformable material, one or more of which contain a susceptor and / or a releaseable component.

[0057] In yet another embodiment, the present invention relates to the matrix particles described above, wherein the matrix material does not contain a susceptor or a releaseable component.

[0058] In one embodiment, the present invention relates to the matrix particles described above, wherein at least one releaseable and / or activable component is a single chemical substance, a combination of chemical substances, an organic chemical substance, and / or an inorganic chemical substance.

[0059] In another embodiment, the present invention relates to the matrix particles described above, wherein the chemical components comprise one or more catalysts, cocatalysts, coreactants, oxidizing agents, reaction inhibitors, accelerators, fuels, explosives, or a combination thereof.

[0060] In yet another embodiment, the present invention relates to matrix particles as described above, wherein when the matrix undergoes deformation, dissolution, melting, expansion, contraction, rupture, plasticization, solvation, or one or more of these, releaseable components are released.

[0061] In one embodiment, the present invention relates to the matrix particle described above, wherein the electromagnetic radiation frequency is in the range of about 300 MHz to about 300 GHz.

[0062] In another embodiment, the present invention relates to the matrix particles described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2,450 MHz.

[0063] In yet another embodiment, the present invention relates to the matrix particles 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 to 10,000 W.

[0064] In another embodiment, the present invention relates to the matrix particle described above, wherein the matrix particle is subjected to the above-mentioned electromagnetic radiation frequency for 10 seconds to 60 minutes.

[0065] In one embodiment, the present invention relates to the matrix particles described above, wherein the matrix is ​​supported by a support comprising, optionally, metal, ceramic, or glass.

[0066] In another embodiment, the present invention relates to the matrix particles described above, wherein the particles are further chemically surface-modified through one or more chemical reactions, optionally comprising a releaseable component, and optionally subsequently forming a partial or complete coating.

[0067] In yet another embodiment, the present invention relates to matrix particles as described above, further having chemical functional groups.

[0068] In one embodiment, the present invention relates to matrix particles as described above, wherein the releaseable component comprises a chemically functional monomer, the matrix material comprises a polymerization material, and optionally the matrix particles are coated with a polymerization coating.

[0069] In another embodiment, the present invention is a process for preparing the matrix particles described above, wherein the process steps are: (i) Emulsification, dispersion, and / or suspension polymerization, (ii) relating to processes including core-shell polymerization.

[0070] In yet another embodiment, the present invention is a process for preparing the matrix particles described above, wherein the process is (i) Coating polymer microparticles with a material containing a susceptor and releaseable components, (ii) Encapsulating microparticles containing susceptors and releaseable components with monomer material, oligomer material, or polymer material. (iii) fusing the susceptor with the releaseable component, and / or (iv) relating to a process that includes sealing a susceptor and releaseable components in external pores on the surface of a porous microsphere or in internal pores within a core.

[0071] In one embodiment, the present invention relates to a process for preparing the matrix particles described above, wherein the process step comprises copolymerization, and the copolymerization step comprises emulsification, dispersion, suspension polymerization, or a combination thereof.

[0072] In one embodiment, the present invention is a process for influencing a chemical reaction, (i) To provide bulk reaction mixtures, (ii) To provide the matrix particles described above, (iii) relating to a process including incorporating matrix particles into a bulk reaction mixture.

[0073] In another embodiment, the present invention is a process for influencing the chemical reaction described above, (iv) The process further comprises thermally activating the susceptor components embedded within the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once.

[0074] In yet another embodiment, the present invention relates to a process for influencing the chemical reactions described above, wherein collisions of RF radiation of at least one frequency and / or MW radiation of at least one frequency are periodically performed, and the period is regular or irregular.

[0075] In one embodiment, the present invention relates to a process for influencing the chemical reaction described above, wherein electromagnetic radiation includes wavelengths in the range of about 1 meter to 1 millimeter and frequencies in the range of 50 MHz to 30 GHz.

[0076] In another embodiment, the present invention relates to a process for influencing the chemical reaction described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2,450 MHz.

[0077] In yet another embodiment, the present invention relates to a process for influencing the chemical reactions 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 to 10,000 W.

[0078] In one embodiment, the present invention relates to a process for influencing the chemical reaction described above, wherein the reaction is a polymerization reaction.

[0079] In another embodiment, the present invention is a process for releasing components that can be released from the matrix particles described above, (a) Dispersing the matrix particles in the bulk reaction mixture, (b) The process comprises bombarding a bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once to thermally activate the susceptor components embedded within the matrix particles.

[0080] In yet another embodiment, the present invention relates to the matrix particles described above, wherein one or more variable matrix materials comprise one or more of wax, polymethyl methacrylate (PMMA), styrene, or one or more polymers or copolymers thereof.

[0081] In one embodiment, the present invention relates to the matrix particles described above, wherein at least one releaseable chemical component comprises an activator or a catalyst.

[0082] In another embodiment, the present invention relates to the matrix particles described above, wherein the catalyst comprises one or more of Cu-acetylacetonate, Cu-2-ethylhexanoate, ferrocene, dimethylaminomethylferrocene, or a combination of one or more thereof.

[0083] In yet another embodiment, the present invention also relates to an article prepared using the process described above.

[0084] In yet another embodiment, the present invention relates to an article prepared using the process described above, wherein all or part of the article is (i) A polymerizable composition of at least one chemical substance or several polymerizable compositions, (ii) reinforced composite articles; (iii) Laminated articles, (iv) rigid laminated articles, (v) flexible laminate article; (vi) foam, or (vii) A combination of those, relating to articles.

[0085] In one embodiment, the present invention also relates to a composition comprising the matrix particles described above, wherein the composition is all or part of an adhesive, sealant, coating, paint, ink, plastic, molded plastic, thermosetting plastic, molded thermosetting plastic, or other polymer-forming composition.

[0086] In another embodiment, the present invention relates to matrix particles as described above, wherein the releaseable and / or activatable component is a catalyst selected from the group consisting of transition metal complexes; transition metal alkoxides; stannous(II) bis(2-ethylhexanoate); carboxylates, alkoxides, and stannous, bismuth, zinc, and titanium complexes; blockized superacids; dodecylbenzenesulfonic acid; dinonylnapthalene sulfonic acid; N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine; organic bases; 1,8-diazabicyclo[5.4.0]undeca-7-ene; 1,5-diazabicyclo[4.3.0]nonene-5); (1,4-diazabicyclo2.2.2-octane); and combinations thereof.

[0087] In one embodiment, the present invention relates to the matrix particles described above, wherein the matrix particles contain carbon nanotubes, and the carbon nanotubes are coated on and / or contained within the matrix particles.

[0088] In one embodiment, the present invention relates to the matrix particles described above, wherein CNTs are incorporated into the matrix particles by a fusion process.

[0089] In one embodiment, the present invention relates to the matrix particles described above, wherein the matrix particles are further coated with a functional nanoparticle emulsion.

[0090] In one embodiment, the present invention relates to the matrix particles described above, wherein the matrix particles are further coated with a monofunctional reactive material.

[0091] In one embodiment, the present invention relates to the matrix particles described above, wherein the matrix particles are further coated with a bireactive material.

[0092] In one embodiment, the present invention relates to a precursor, intermediate, or final monomer composition, oligomer composition, or polymer composition comprising the matrix particles described above.

[0093] In one embodiment, the present invention relates to a precursor, intermediate, or final monomer, oligomer, or polymer composition containing matrix particles as described above, wherein the composition is prepared from a functionalized polymer formulation.

[0094] In one embodiment, the present invention relates to a precursor, intermediate, or final monomer, oligomer, or polymer composition comprising matrix particles as described above, wherein the composition is prepared as a reactive blend with a non-reactive polymer or oligomer.

[0095] In one embodiment, the present invention is a process for influencing a chemical reaction, (i) To provide bulk reaction mixtures, (ii) To provide the matrix particles described in any one of the prior claims, (iii) Incorporating matrix particles into the bulk reaction mixture, (iv) Thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once, The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for solid-phase polymerization.

[0096] In one embodiment, the present invention is a process for influencing a chemical reaction, (i) To provide bulk reaction mixtures, (ii) To provide the matrix particles described above, (iii) Incorporating matrix particles into the bulk reaction mixture, (iv) Thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once, The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive hot melt formulation.

[0097] In one embodiment, the present invention is a process for influencing a chemical reaction, (i) To provide bulk reaction mixtures, (ii) To provide the matrix particles described above, (iii) Incorporating matrix particles into the bulk reaction mixture, (iv) Thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once, The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a functionalized polymer formulation.

[0098] In one embodiment, the present invention is a process for influencing a chemical reaction, (i) To provide bulk reaction mixtures, (ii) To provide the matrix particles described above, (iii) Incorporating matrix particles into the bulk reaction mixture, (iv) Thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once, The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive blend with a non-reactive polymer or oligomer.

[0099] In one embodiment, the present invention relates to the process described above, wherein collisions of RF radiation of at least one frequency and / or MW radiation of at least one frequency are carried out periodically, and the period is regular or irregular.

[0100] In another embodiment, the present invention relates to the process described above, wherein the electromagnetic wave includes wavelengths in the range of about 1 meter to 1 millimeter and frequencies in the range of 50 MHz to 30 GHz.

[0101] In yet another embodiment, the present invention relates to the process described above, wherein the electromagnetic radiation frequency is in the range of about 915 MHz to about 2,450 MHz.

[0102] In one embodiment, the present invention relates to the process 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 to 10,000 W.

[0103] In another embodiment, the present invention relates to the process described above, wherein electromagnetic radiation collides for 10 seconds to 60 minutes.

[0104] In yet another embodiment, the present invention relates to the process described above, wherein the reaction is a polymerization reaction.

[0105] In one embodiment, the present invention relates to a process for increasing the overall loading amount of CNTs in a reaction mixture by the process described above.

[0106] In one embodiment, the present invention relates to a process for maintaining lower viscosity when adding an additive to a reaction mixture, the process comprising incorporating the additive into the matrix particles described above and incorporating the matrix particles into a bulk reaction mixture.

[0107] In one embodiment, the present invention is a process for increasing the overall load of an additive in a chemical reaction, (i) To provide bulk reaction mixtures, (ii) To provide matrix particles containing the additives described above, (iii) Incorporating matrix particles into the bulk reaction mixture, (iv) Thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once, The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive hot melt formulation.

[0108] In one embodiment, the present invention is a process for maintaining lower viscosity when adding an additive to a reaction mixture, comprising reducing van der Waals forces between the additive and the bulk reaction mixture, comprising: incorporating the additive into the matrix particles described above; incorporating the matrix particles into the bulk reaction mixture; and thermally activating the susceptor components embedded in the matrix particles by 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. The present invention relates to a process in which the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive hot melt formulation.

[0109] Surprisingly, nanoparticles and microparticles have been found to function as carriers for more effectively delivering nanomaterials to sealants, coatings, composites, adhesives, and other polymer products. Particularly interesting is when the physical properties of the final composition and / or physical product are achieved, including, but not limited to, thermal and electrical conductivity, improved and / or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy decay, and improved or controlled product life and / or failure.

[0110] The present invention specifically relates to particles that support, are filled with, or otherwise support layers of nanomaterials, including, but not limited to, metals and their chemical products, graphene, nanotubes and similar structures, in order to minimize the need for a more significant amount of such nanomaterial, for example, to benefit from improved physical, electrical, conductive and other similar properties.

[0111] Optionally, crosslinking chemistry can be incorporated into or on the surface of the particles, either simply using surface chemistry, or as a ligand or oligomer-like structure that can even further enhance the physical properties described.

[0112] Specifically, structures such as nanotubes, specifically nanomaterials such as carbon nanotubes and / or graphene, can be incorporated into polymer particles, and / or polymer particles can be coated with nanomaterials. This basic concept helps, among other things, limit the overall amount of material required, can provide a large surface area containing the structure in which separating forces are dispersed, and can limit aggregation, etc. When nanoparticles and / or microparticles are coated with coatings that improve van der Waals forces and other physical or chemical forces, these effects can be further improved and / or amplified and controlled, if desired.

[0113] The literature describes, for example, the coating of such particles with carbon nanotubes or the coating of individual nanotubes. Here, we differentiate by coating the particles with nanotubes and then coating them with a force-improving composition, incorporating two or more, preferably three or more nanotubes and / or coating them with the force-improving composition.

[0114] Optionally, any chemical functional groups for subsequent reactions or physical effects can be incorporated into the particles and / or their coatings. Examples of chemical reactions are numerous and not limited to crosslinking and / or polymerization reactions. Physical effects include, for example, ligand, polymer, or oligomer structures by physical combination with a surrounding polymer matrix, or, in the case of metal or soap-like ligands, by dispersion or inclusion in emulsions, dispersions, etc., in solvents, water, or other substances. Optional inclusion of catalysts, co-catalysts, accelerators, fuels, energy materials, etc.—incorporated by reference as fully described herein, see U.S. Patent Application No. 18 / 055,302 by Malofsky et al.

[0115] An additional object of the present invention is to provide polymer nanoparticles and microparticles having functional groups on their surface that can be irreversibly / reversibly reduced when a composition containing polymer microparticles is applied to a composition containing sealants, composites, adhesives, other polymer products, etc.

[0116] Another objective is to provide functional groups capable of hydrogen bonding or non-covalent bonding such as van der Waals when compositions containing polymer microparticles are applied to compositions for sealants, composites, adhesives, and other polymer products.

[0117] Generally, these functional nanoparticles and microparticles are versatile platforms with tunable properties that can be adjusted to meet specific application requirements. These functional nanoparticles and microparticles are used in a wide range of applications, including adhesives, composites, laminates, sealants, coatings, inks, and plastics, in numerous end products across many consumer, industrial, and / or medical applications.

[0118] Functional nanomicroparticles include, but are not limited to, latex particles, nano and microgel particles, and colloidal particles composed of polymer chains dispersed in water or other solvents. They also include microgel particles that can swell or contract in response to changes in the environment.

[0119] Functional microparticles containing reactive functional groups such as carboxylic acids, amino groups, thiols, epoxy, acrylic, and isocyanates can be crosslinked with other functional particles.

[0120] In coatings, crosslinked polymer microparticles are used to produce compositions containing a high solid content and / or to improve rheological properties.

[0121] Polymers containing 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 their inherent advantages, polymers have several drawbacks, including low mechanical strength, low hardness, high water sensitivity, and thermal softening. Water-based reactions are relatively slow and can also cause health problems due to the release and use of hydrazine, formaldehyde, and other toxic chemicals.

[0122] In addition to creating polymer particles that can be dispersed in liquids, surface functional groups eliminate the need for slow reactivity and the use of toxic chemicals to accelerate the reaction.

[0123] In the core-shell configuration, the nanomaterials present in the core and the crosslinking functional groups on the shell help protect the CNTs until secondary processing is performed. The released nanomaterials increase interaction and crosslinking density due to van der Waals forces.

[0124] In another aspect of the present invention, the present invention provides a microparticle composition comprising a nanomaterial in the core, a catalyst, a crosslinking agent, and functional groups on the shell. Further objects of the present invention can be achieved by generating microparticles having particle sizes in the range of 0.01 to 10 microns, and by modifying existing microparticles.

[0125] A further object of the present invention can be achieved by generating nanoparticles and microparticles having particle sizes in the range of 0.01 to 100 microns, including modifying existing microparticles.

[0126] The polymer microparticles of the present invention are manipulated to specific shapes, sizes, and surface chemistry so that hybrids of organic and inorganic materials can be created.

[0127] A further aspect of the present invention provides a method for producing crosslinked polymer microparticles in which nanomaterials are embedded. The crosslinked microparticles can be delivered in a masterbatch or as standalone particles.

[0128] A covalent adaptable network (CAN) is a polymer material that has covalent bonds that can be broken and reformed under certain conditions. Materials with reversible or tunable properties such as mechanical strength or viscosity can be developed in this manner.

[0129] The low entropy of the functional groups on the microparticles improves the chances of CAN formation compared to conventional crosslinking agents. Carbon nanotubes and graphene on the surface of the functional microparticles provide additional adhesion sites for CAN formation.

[0130] These crosslinkable, reversible groups attached to microparticles help create self-healing coatings, adhesives, composites, and structural materials via CAN.

[0131] The functional groups (pressure-sensitive adhesives) on the microparticles used in PSAs improve their tackiness and allow them to adhere easily to surfaces. Functional microparticles provide additional contact points between the adhesive and the substrate, reducing the possibility of creep failure over time.

[0132] The addition of nanomaterials with high elastic modulus, such as CNTs and graphene, improves resistance to deformation.

[0133] Pressure causes the functional particles to break down in the PSA, releasing chemicals that promote further crosslinking with the substrate and improve adhesion. Functional microparticles provide an adjustable bond line thickness. Microparticles can, for example, increase the viscosity of the adhesive, which improves its shear strength and prevents it from flowing.

[0134] Further aspects of the present invention relate to superior thermal and electrical conductivity by incorporating materials with lower viscosity by using materials more efficiently and creating an apparent honeycomb network that enables the final polymer-based high-conductivity product. [Brief explanation of the drawing]

[0135] In the drawings, they are not necessarily drawn to scale, and similar numbers may be used to describe similar components in different drawings. Similar numbers with different letter suffixes may represent different instances of similar components. These drawings illustrate the various aspects considered in this document in general terms, not as limitations. [Figure 1] A schematic diagram of the process of the present invention is shown. [Figure 2A] The diagrams show currently available reaction injection molding processes and the simplified process according to the present invention, respectively. [Figure 2B] The diagrams show currently available reaction injection molding processes and the simplified process according to the present invention, respectively. [Figure 3A] These examples show currently available film lamination adhesives and the simplified process resulting from the present invention. [Figure 3B] These examples show currently available film lamination adhesives and the simplified process resulting from the present invention. [Figure 4] This specification shows exemplary general structures of the matrix and coated matrix of the present invention as intended herein. [Figure 5A] This specification shows an exemplary compositional structure of the matrix of the present invention as intended herein. [Figure 5B] This specification shows an exemplary compositional structure of the matrix of the present invention as intended herein. [Figure 6] This specification illustrates exemplary matrices and coated matrices of the present invention as intended. The matrices can be coated onto an object or located within a coating on various objects. [Figure 7] A scanning electron micrograph (SEM) image of an exemplary hollow particle is shown. [Figure 8] An exemplary SEM image of a hollow particle + SPION + copper is shown. [Figure 9] This image shows a SEM image of commercially available PMMA (MX500-ML, Soken) coated with carbon nanotubes (CNTs). [Figure 10] This is a graph of the heating curve using a carbon nanostructure (CNS) susceptor. [Figure 11] This figure shows the selective arrangement of susceptors within the shell on a particle according to the present invention. [Figure 12] This figure shows a sheet created through non-covalent interactions. [Figure 13] This diagram shows a schematic representation of the functionalized carbon nanotubes located within the shell of the particles of the present invention. [Figure 14] The diagram shows the microparticles after functionalization for chelation of the catalyst. [Figure 15] A schematic diagram illustrating the containment of CNTs and susceptors using micellar microparticles is shown. [Figure 16] A schematic diagram illustrating the containment of microparticles within micelles and catalysts on carbon nanotubes (CNTs) is shown. [Figure 17] This diagram illustrates catalyst chelation and susceptor containment using micellar microparticles. [Figure 18] This shows core-shell particles produced using a commercially available aqueous emulsion. [Figure 19]This shows matrix particles (cores) that act as carriers for delivering CNTs to different matrices. [Figure 20] The plot of electrical resistivity against CNS filling amount shows a steady-state decrease in electrical resistivity from 1.0 × 10¹³ to 6.0 × 10³ ohms for CNT filling amounts of 0 to 3.2%. [Modes for carrying out the invention]

[0136] Generally speaking, in one embodiment, the present invention relates to matrix particles comprising a matrix material as defined below, a susceptor, and a releaseable component. In some embodiments, these particles have a core-shell structure, or are simply cores. The core is capable of changing its physical or chemical form, thereby enabling the release of the releaseable component. If the particle has a core-shell structure, one or more shells may be present. The susceptor may not be present in the shells, or may be present in one or more shells. Similarly, the releaseable component may not be present in the shells, or may be present in one or more shells. Thus, the shells are physically or chemically modifiable materials, such as oligomers or polymer materials. The presence of a susceptor in the matrix particles is optional. Such matrix particles are mixed into a target physical or chemical composition that needs to be physically or chemically affected by applying an external force, such as high frequency or heat, which mixes with the matrix particles, modifies the matrix particles, and releases the releaseable component into the physical or chemical mixture or composition.

[0137] This invention generally relates to matrix microparticles and nanoparticles. Although this invention is discussed herein in terms of microparticles, it is equally applicable to nanoparticles.

[0138] A plurality of matrix particles comprising matrix particle A and / or matrix particle B, wherein matrix particle A comprises a core and optionally at least one shell, the core comprising (i) a matrix material capable of completely or partially altering its physical and / or chemical properties, (ii) at least one susceptor component, the at least one susceptor component embedded in the matrix material, and (iii) at least one emittable component, the at least one emittable component embedded in the matrix material, and the at least one emittable component in contact with the plurality of matrix particles A shell comprising (iv) optionally, at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, and (v) at least one releaseable component being embedded in the at least one shell, the at least one releaseable component being capable of physically or chemically influencing the bulk physically 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 is (vi) a matrix material which is capable of completely or partially altering its physical and / or chemical properties, and (vii) at least one emittable component which is embedded in the matrix material which is capable of physically or chemically influencing the bulk physically or chemically modifiable composition in which the plurality of matrix particles come into contact, and the at least one shell is (viii) optionally at least one susceptor component, The present invention relates to a plurality of matrix particles comprising: (ix) at least one susceptor component, the at least one susceptor component being embedded in the at least one shell; and (ix) at least one emittable component, the at least one emittable component being embedded in the at least one shell, and the at least one emittable component being capable of physically or chemically influencing a physically or chemically modifiable bulk composition in contact with the plurality of matrix particles, wherein the at least one susceptor component and / or emittable component can be activated through radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical polishing, or a combination thereof.

[0139] In one embodiment, the present invention relates to a plurality of matrix particles including matrix particle A, wherein the matrix particle A comprises a core and optionally at least one shell, and the core is (i) A matrix material which is capable of completely or partially altering its physical and / or chemical properties, (ii) at least one susceptor component, the at least one susceptor component being embedded in the matrix material, (iii) at least one releaseable component, the at least one releaseable component embedded in the matrix material, the at least one releaseable component capable of physically or chemically influencing a bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, the at least one shell, (iv) Optionally, the at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, (v) comprising at least one releaseable component, the at least one releaseable component embedded in the at least one shell, the at least one releaseable component capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, The present invention relates to a plurality of matrix particles, wherein at least one susceptor component and / or emittable component can be activated through radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical polishing, or a combination thereof.

[0140] In another embodiment, the present invention relates to a plurality of matrix particles, each matrix particle B comprising a core and optionally at least one shell, wherein the core (vi) A matrix material which is capable of completely or partially altering its physical and / or chemical properties, (vii) at least one releaseable component, the at least one releaseable component embedded in the matrix material, the at least one releaseable component capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, the at least one shell, (viii) Optionally, the at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, (ix) relating to a plurality of matrix particles, comprising the at least one emittable component, the at least one emittable component embedded in the at least one shell, the at least one emittable component capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, wherein the at least one susceptor component and / or emittable component can be activated through radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical polishing, or a combination thereof.

[0141] In one embodiment, the present invention comprises a plurality of matrix particles including matrix particle A and / or matrix particle B, The matrix particle A comprises a core and, optionally, at least one shell. The core in question, (i) A matrix material which is capable of completely or partially altering its physical and / or chemical properties, (ii) at least one susceptor component, the at least one susceptor component being embedded in the matrix material, (iii) at least one releaseable component, the at least one releaseable component being embedded in the matrix material and capable of physically or chemically influencing the physical or chemical composition in which the plurality of matrix particles come into contact, The at least one shell, (iv) the at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, (v) at least one releaseable component, the at least one releaseable component being embedded in the at least one shell, and the at least one releaseable component being capable of physically or chemically influencing the physical or chemical composition in which the plurality of matrix particles come into contact, and The matrix particle B comprises a core and optionally at least one shell, and the core is (vi) A matrix material which is capable of completely or partially altering its physical and / or chemical properties, (vii) at least one releaseable component, the at least one releaseable component embedded in the matrix material, the at least one releaseable component capable of physically or chemically influencing the bulk physical or chemical composition in contact with the plurality of matrix particles, the at least one shell, (viii) the at least one susceptor component, the at least one susceptor component being embedded in the at least one shell, (ix) relating to a plurality of matrix particles comprising at least one emittable component, the at least one emittable component being embedded in the at least one shell, the at least one emittable component being capable of physically or chemically influencing a physical or chemical composition in contact with the plurality of matrix particles, wherein the at least one susceptor component and / or emittable and / or activatable component can be activated through radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical polishing, or a combination thereof.

[0142] In another embodiment, the matrix particles are in contact with a chemical reaction mixture containing constituent reactants that are likely to undergo a chemical reaction, or are incorporated into or dispersed within monomers or oligomers of a polymerization reaction, for example. In a further embodiment of the present invention, the chemical reaction mixture containing dispersed matrix particles is collided with or heated by high-frequency electromagnetic radiation or microwave radiation, or mechanically polished. EMR (Electromagnetic Radiation) heats the susceptor components within the matrix particles. This heating then releases active components that subsequently catalyze the reaction in the reaction mixture. Thus, the reaction is initiated only when RF or MW radiation releases components from the matrix particles.

[0143] In another embodiment, the matrix particles are in contact with, incorporated into, or dispersed in a chemical mixture, and the components may or may not undergo chemical changes upon contact with the matrix particles, but undergo physical changes, such as changes in viscosity, upon release of emittable and / or activatable components via RF / MF radiation or heating or mechanical polishing.

[0144] definition A “variable matrix” or “variable matrix” means that the matrix material within the matrix particles can be completely or partially deformed, dissolved, melted, expanded, contracted, burst, plasticized, or solvated. In other words, its physical and / or chemical form can be altered to facilitate the release of active ingredients.

[0145] "Susceptor" refers to a particle within a matrix that is easily heated or thermally activated by electromagnetic radiation, particularly high-frequency and / or microwave radiation.

[0146] "To affect a chemical reaction" means that the releaseable component can activate or induce, catalyst, co-catalyze, promote, accelerate, co-accelerate, inhibit, and / or heat a chemical reaction.

[0147] "Matrix material" or "matrix" means the base material of matrix particles into which susceptor components and / or releaseable and / or activateable components are embedded. The base material may be, for example, a monomer, oligomer, or polymer.

[0148] "Embedded" means that the susceptor, or releaseable and / or activatable component, is encapsulated or contained within the matrix material, for example, in close contact with or associated with the matrix within the pores of the matrix, or bonded to one or more matrix materials and may be present within the matrix or on one or more surfaces of the matrix material, may be completely encapsulated within the matrix material, or may be partially embedded within matrix particles by physical adhesion, or may partially protrude from the surface of matrix particles.

[0149] "Matrix particles" means nanoparticles or microparticles comprising a matrix material, a susceptor component, and a releaseable and / or activatable component used for thermal activation of the bulk reaction mixture described in the present invention. In some embodiments, the susceptor component may be absent. In some embodiments, the susceptor itself may be the releaseable and / or activatable component.

[0150] "EM" refers to high-frequency electromagnetic radiation such as radio waves (RF) or microwaves (MW).

[0151] "Releasable and / or activatable components" refers to components contained within the matrix microparticles that play a role in influencing chemical reactions during the remote thermal activation of susceptors within the matrix particles, and subsequently releasing or activating the releasable and / or activatable components. Instead of the term "releasable and / or activatable components," the terms "active component" or "releasable component" are used. In other words, the active component embodies its release and activation characteristics. The active component is the activating chemical component in many embodiments, as described below.

[0152] A "bulk reaction mixture" refers to a reaction mixture in which the release of the active ingredient can be affected by matrix particles. In a bulk reaction mixture, the matrix particles are dispersed, and then the susceptors are remotely activated to release the active ingredient, for example, catalyzing the bulk reaction mixture. For example, a bulk reaction mixture may be a prepolymerization material and a postpolymerization material to increase the molecular weight, such as any other chemical reaction, such as an organic or inorganic, or organic-inorganic combined reaction. A bulk reaction mixture may be transparent, translucent, or opaque. Alternatively, the transparency of a bulk reaction mixture may change as the reaction proceeds.

[0153] When used in the context of reaction mixtures, “precursor” means a reaction mixture that is likely to proceed to its next form, the “intermediate” reaction mixture. In one embodiment, the precursor reaction mixture may be a monomer, oligomer, polymer, or a mixture of one or more.

[0154] When used in the context of reaction mixtures, “intermediate” means a reaction mixture that is chemically and / or physically converted to the next phase, which can be further chemically and / or physically converted to the final phase of the reaction. In one embodiment, the intermediate reaction mixture may be a monomer, oligomer, polymer, or a mixture of one or more.

[0155] "Core" refers to the portion of the matrix particle that contains the matrix material and into which the susceptor and / or releaseable components are embedded.

[0156] The term "shell" refers to the portion of matrix particles that completely or partially encloses the core. It may be composed of monomer, oligomer, or polymer material and may have a susceptor and / or releaseable component embedded therein. The shell is modifiable in that it can allow for the release of the releaseable component. In one embodiment, the shell may act as a force modifier at the point of introducing matrix particles into a chemical or physical mixture that needs to be chemically and / or physically modified. Subsequently, the shell may be modifiable by external forces, if necessary, for example, through RF, MF, mechanical shear, heat, or a combination of these techniques. In one embodiment, the shell is also made from a matrix material similar to or different from the core.

[0157] "Polymer brush particles" refer to particles that have a dense layer of polymer chains attached to their surface and whose appearance resembles a brush.

[0158] "Bulk physical or chemical composition" means a chemical composition that is understood in the art to have physical and chemical properties. The term "physical composition" may be used only to indicate that the physical properties are susceptible to change. A chemical composition, as used herein, may be susceptible to change in at least one chemical property.

[0159] "Physically or chemically affecting the physical or chemical composition of the bulk" means that the incorporation of matrix particles alters at least one physical or chemical property of the bulk. Alternatively, if a releaseable component were added without using the matrix particle configuration of the present invention, the one physical or chemical property that would have been altered would be maintained.

[0160] The precursor or intermediate may be transformed by standard chemical or physical procedures and / or by RF and / or MW frequency collisions as described herein.

[0161] In another embodiment, the present invention relates to a process for incorporating matrix particles into a chemical reaction mixture in order to influence a chemical reaction. For example, the matrix particles may be dispersed in a monomer mixture before polymerization. In another embodiment, the present invention relates to activating a chemical reaction, such as a polymerization reaction, by heating the susceptors of matrix particles with electromagnetic radiation (EMR), such as radio frequency (RF) or microwave (MW) radiation, and then releasing or activating releaseable and / or activateable components. Alternatively, thermal and mechanical abrasion, such as shearing, may be used to release releaseable components.

[0162] This disclosure relates to materials and methods for carrying out chemical reactions, such as polymerization reactions in which the chemical events are uniformly and activated as required. The reactions envisioned herein do not require heating of the entire reaction material mass and can be achieved not limited to light such as infrared, ultraviolet, or visible light transmission, particularly for highly packed material masses, opaque material masses, etc.

[0163] In some embodiments, the present invention relates to materials and methods for polymerization that do not require mixing of two reaction components, or in some embodiments, involve mixing of two components but do not have an immediate or rapid reaction, and / or have the ability to delay the reaction as required. For example, some embodiments of the present disclosure provide low molecular weight and high performance materials for reducing curing time in polymerization to minutes or hours, and curing time in mold making to days or weeks. In one embodiment, the present invention can inhibit chemical events by activating chemical components.

[0164] In some embodiments, the present disclosure provides materials and methods for polymerization that reduce or eliminate the need for higher molecular weight materials, which would consequently require high temperatures and pressures in injection molding and reaction injection molding, for example, and instead allow for molecular weight increases during the process or in the mold, and as required. Preferably, the matrix particles have a low molecular weight matrix material. The low molecular weight matrix particles of the present invention provide uniform mixing of fillers and provide higher performance adhesion without undesirable rheological problems. The present invention enables less complex apparatus and curing as required, simplifying the preparation, storage, packaging, and handling of materials.

[0165] The low molecular weight matrix particles provided herein can be applied as adhesives to a variety of materials for various applications. The present invention also provides local heating or thermal activation. The matrix particles described herein provide the ability to activate polymerization as required. Polymerization provided herein may be activated through a substrate, filler, other additives, etc. In other words, opacity or lack of transparency of the bulk chemical mixture or porous polymerization mixture does not significantly affect the progress of the reaction. The low molecular weight matrix particles described herein provide polymerization that does not depend on overall heating or thermal activation.

[0166] The low molecular weight material of the present invention, i.e., 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 both two-dimensional and three-dimensional selective activation.

[0167] In some embodiments, the matrix particles described herein provide a polymerization for adhesives for producing processed articles, comprising a rigid and / or flexible laminate having two or more layers. In some embodiments, the matrix particles described herein provide a polymerization for adhesives for pressure-sensitive materials and related articles thereof.

[0168] In one embodiment, the low molecular weight matrix particles of the present disclosure provide improved curing for adhesives, coatings, and the like. This also includes substrates through which energy passes, such as highly packed material masses and opaque material masses.

[0169] Embodiments of the present invention provide materials and methods for improved nonmetallic molding, polymer molding, and high-speed mold making and delivery.

[0170] This process can also be carried out under ambient conditions. Thermal activation to induce localized chemical events is achieved by applying electromagnetic radiation (EMR), such as radio frequency (RF) radiation or microwave (MW) radiation. The present invention is applicable to bonding polymer substrates such as elastomer substrates and rigid substrates, including fabrics and laminates.

[0171] For example, a matrix that melts, melts, expands, cracks, bursts, and / or deforms due to heating of susceptor components such as carbon nanotubes releases or activates chemical components such as catalysts, which then catalyze a reaction, such as a polymerization reaction or a rapid energy generation reaction.

[0172] In another embodiment, the present invention relates to a matrix particle, (i) Matrix material, wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties, and (ii) at least one susceptor component, the at least one susceptor component being embedded in the matrix material, and / or at least one releaseable component embedded in the matrix material, the at least one releaseable component being capable of influencing a chemical reaction, The present invention relates to matrix particles in which at least one susceptor component and / or emittable component can be thermally activated through radio frequency (RF), microwave (MW) radiation, thermal activation, or mechanical polishing.

[0173] In other words, in one embodiment, the matrix particles include either a susceptor component or a releaseable material, or both. For example, carbon nanostructures such as CNTs or graphene can act as susceptors and can be releaseable components.

[0174] In one embodiment, since activation may or may not be required via RF or MF when activation is initiated thermally or via mechanical polishing, there are no susceptor components.

[0175] In one embodiment, the matrix particles include a core, the core itself acting as the matrix material. The core includes carbon nanostructures that are releasably attached to, embedded in, or incorporated within the core. The core is made of an organic material, such as an oligomer or polymer. For example, the core is made of wax, as described elsewhere.

[0176] In another embodiment, the matrix particle includes a core and a shell. The core, shell, or core and shell together constitute the matrix material. The matrix material includes carbon nanostructures that are releaseably attached to, embedded in, or incorporated within the matrix material. The core is made of an organic material, such as an oligomer or polymer. For example, as described elsewhere, the core is made from wax. Examples of organic materials include polymer materials and oligomeric materials. The shell, if present, is made of an organic material such as an oligomer or polymer, thereby enabling deformation and release of releaseable components.

[0177] Nano- and micro-sized matrix particles can function as carriers for more effectively delivering nanomaterials within sealants, coatings, composites, adhesives, and other polymer products (see U.S. Patent Application No. 2023 / 0285948(A1), which is incorporated by reference in whole). Of particular interest are cases where physical properties of the final composition or physical product are achieved, including, but not limited to, thermal and electrical conductivity, improved or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy decay, and improved or controlled product life and failure.

[0178] The present invention relates to matrix particles containing nanomaterials, including metals and their chemical products, graphene, and carbon nanostructures such as carbon nanotubes, which can improve physical, electrical, and conductive properties, and can easily provide larger quantities of the nanomaterials.

[0179] 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 that can further enhance the described physical properties.

[0180] Specifically, polymer particles containing nanomaterials such as carbon nanotubes or carbon nanostructures like graphene can be incorporated internally or coated. This basic concept is useful, among other things, for limiting the total amount of material required, providing a large surface area containing the structure through which separating forces diffuse, and limiting aggregation. When the matrix particles are coated with a coating that modifies van der Waals forces and other physical or chemical forces, these effects can be further improved, amplified, and controlled as desired.

[0181] In one aspect of the present invention, particles are coated with nanotubes, then coated with a force-improving composition incorporating two or more, preferably three or more nanotubes, and subsequently, optionally, coated with another force-improving composition.

[0182] Optionally, any chemical functional groups for subsequent reactions or physical effects can be incorporated into the particles or their coatings. Examples of chemical reactions are numerous and not limited to crosslinking and / or polymerization reactions. Physical effects include, for example, ligand, polymer, or oligomer structures formed by physical combination with a surrounding polymer matrix, or, in the case of metal or soap-like ligands, by dispersion or inclusion in emulsions, dispersions, etc., in solvents, water, or other substances. Optional inclusion of catalysts, co-catalysts, accelerators, fuels, energy materials, etc., is also included in the invention.

[0183] An additional object of the present invention is to provide polymer nanoparticles and microparticles having functional groups on their surface that can be irreversibly / reversibly reduced when a composition containing polymer microparticles is applied to a composition containing sealants, composites, adhesives, other polymer products, etc.

[0184] Another objective is to provide functional groups capable of hydrogen bonding or non-covalent bonding such as van der Waals when compositions containing polymer microparticles are applied to compositions for sealants, composites, adhesives, and other polymer products.

[0185] Generally, these functional nanoparticles and microparticles are versatile platforms with tunable properties that can be adjusted to meet specific application requirements. These functional nanoparticles and microparticles are used in a wide range of applications, including adhesives, composites, laminates, sealants, coatings, inks, and plastics, in many end products across numerous consumer, industrial, and / or medical applications.

[0186] Functional microparticles containing reactive functional groups such as carboxylic acids, amino groups, thiols, epoxy, acrylic, and isocyanates can be crosslinked with other functional particles.

[0187] Polymers containing functional microparticles, such as water-based polyurethanes (WPU), polyester dispersions (PEDs), and polyacrylate emulsions (PAEs), are commonly used in wood coatings, metal coatings, printing inks, architectural coatings, and plastic coatings. Despite their inherent advantages, polymers have several drawbacks, including low mechanical strength, low hardness, high water sensitivity, and thermal softening. Water-based reactions are relatively slow and can also cause health problems due to the release and use of hydrazine, formaldehyde, and other toxic chemicals.

[0188] In addition to creating polymer particles that can be dispersed in liquids, surface functional groups eliminate the need for slow reactivity and the use of toxic chemicals to accelerate the reaction.

[0189] In the core-shell configuration, the nanomaterials present in the core and the crosslinking functional groups on the shell help protect the CNTs until secondary processing is performed. The released nanomaterials increase interaction and crosslinking density due to van der Waals forces.

[0190] In another aspect of the present invention, the present invention provides a microparticle composition comprising a nanomaterial in the core, a catalyst, a crosslinking agent, and functional groups on the shell. Further objects of the present invention can be achieved by generating microparticles having particle sizes in the range of 0.01 to 10 microns, and by modifying existing microparticles.

[0191] A further object of the present invention can be achieved by generating nanoparticles and microparticles having particle sizes in the range of 0.01 to 100 microns, including modifying existing microparticles.

[0192] The polymer microparticles of the present invention are manipulated to specific shapes, sizes, and surface chemistry so that hybrids of organic and inorganic materials can be created.

[0193] A further aspect of the present invention provides a method for producing crosslinked polymer microparticles in which nanomaterials are embedded. The crosslinked microparticles can be delivered in a masterbatch or as standalone particles.

[0194] Covalently adaptable networks (CANs) are polymer materials that have covalent bonds that can be broken and reformed under certain conditions. Materials with reversible or tunable properties such as mechanical strength or viscosity can be developed in this manner.

[0195] The low entropy of the functional groups on the microparticles improves the chances of CAN formation compared to conventional crosslinking agents. Carbon nanotubes and graphene on the surface of the functional microparticles provide additional adhesion sites for CAN formation.

[0196] These crosslinkable, reversible groups attached to microparticles help create self-healing coatings, adhesives, composites, and structural materials via CAN.

[0197] The functional groups (pressure-sensitive adhesives) on the microparticles used in PSAs improve their tackiness and allow them to adhere easily to surfaces. Functional microparticles provide additional contact points between the adhesive and the substrate, reducing the possibility of creep failure over time.

[0198] The addition of nanomaterials with high elastic modulus, such as CNTs and graphene, improves resistance to deformation.

[0199] Pressure causes the functional particles to break down in the PSA, releasing chemicals that promote further crosslinking with the substrate and improve adhesion. Functional microparticles provide an adjustable bond line thickness. Microparticles can, for example, increase the viscosity of the adhesive, which improves its shear strength and prevents it from flowing.

[0200] Further aspects of the present invention relate to superior thermal and electrical conductivity by incorporating materials with lower viscosity by using materials more efficiently and creating an apparent honeycomb network that enables the final polymer-based high-conductivity product.

[0201] The ability to heat a composition and, as required and with low to insignificant additional energy input, release catalysts, co-catalysts, accelerators, or other reaction-initiating compounds enables novel processes, materials, and subsequent products and processes that were previously unattainable, specifically with respect to hot-melt adhesives, molding, preforms, plastics for thermoplastic molding, and overmolding of dissimilar materials. In the overmolding process, the adhesive layer functions to enable compatibility between thermoplastic and thermosetting properties.

[0202] Specifically, the present invention relates to carbonaceous susceptor particles coated with a material capable of preventing strong van der Waals force interactions, and / or the addition of individual carbonaceous susceptors or clusters of carbonaceous susceptors coated with a material capable of preventing van der Waals interactions, so as to significantly minimize or eliminate the effects of van der Waals forces, and in particular enable the easy addition of the material at high concentrations, thereby facilitating RF heating and causing easy physical deformation, including softening or melting. The aforementioned coating significantly reduces aggregation or other macrostructures that can cause a significant increase in viscosity or similar physical effects. The coating can slow down, stop, or prevent thermal, electrical, or other similar effects where desired. The aforementioned compositions can be easily mixed with existing formulations using conventional equipment.

[0203] The applications of hot melt adhesives illustrate the overall possible effects, which can be extended to other products containing materials ranging from low molecular weight materials and bio-derived temperature-sensitive renewable materials to high molecular weight thermoplastic resins and polymers.

[0204] Specifically, the van der Waals effect is minimized, viscosity is significantly reduced throughout the temperature range, and it becomes possible to incorporate more of the coated material, so that carbonaceous materials can be coated as individual, cluster, coated particles, and optionally, other combinations incorporating other materials.

[0205] In one embodiment, the present invention facilitates RF heating, particularly microwave heating, to enable higher filling of the material in order to promote ease of processing and / or a high level of reinforcement. As described in the background art above, other objectives may include thermal or electrical conductivity, reaction initiation, CTE matching, thermal conductivity through particles, and the like.

[0206] The preform, in any of the properties described above, or in a selection of reactive materials using particles containing catalysts such as those described in Malofsky et al. U.S. Patent Application No. 18 / 055,302, includes another exemplary group of applications that allow the carbonaceous material to be initially added to a polymer in a molten material to initiate a reaction in which the particles maintain their integrity at the formation or deformation temperature during part fabrication processing until RF heating is performed to a higher temperature for release or exposure by catalyst or other means and subsequent activation. RF heating enables rapid manufacturing for high throughput and lower cost. Such a process in certain applications may eliminate the need for cooling of the B-stage preform or material.

[0207] The layers for plastic injection molding, blow molding, and thermal bonding (extrusion) of polymer or polymer-coated layers functioned similarly to those described above.

[0208] The advantages of additional reinforcing materials such as carbon, glass, aramid, ultra-high molecular weight polyethylene, as well as natural and synthetic fibers, and other combinations, are demonstrated in multiple ways.

[0209] This method offers the advantages of ease of addition and lower viscosity.

[0210] Examples of applications include reinforced hot melts; reactive hot melts; continuous or discontinuous hot melt coated articles, webs, and films; continuous or discontinuous hot melt coated fibers; and hot melt adhesive articles, including fibers, ropes, shapes, dots, and preform articles made from monomers, polymers, and / or oligomers.

[0211] One of the advantages is that it adheres to the substrate with minimal excess adhesive material.

[0212] Minimizing polymerization energy and precise polymerization control In one embodiment, the present invention also relates to minimizing the energy required to activate chemical reactions and their effects, specifically avoiding total heating, for example, limited energy transmission when using UV light, and the ability to activate one or more chemical events as desired in any order or sequence to achieve a desired result.

[0213] Activation of chemical reactions and polymerization through opaque objects Uncontrolled, rapid reactions in UV curing chemistry can result in highly crosslinked systems. In some applications requiring toughness, uncontrolled UV curing reactions lead to undesirable vitrification and brittleness. Embodiments of the present invention provide a uniform distribution of catalyst / co-catalyst as components of the matrix particles in the reaction mixture. While not theoretically bound, this uniform distribution in the reaction mixture allows for the simultaneous initiation of polymerization reactions at multiple sites, which contributes to the creation of a homogeneous polymer network. While not theoretically bound, simultaneous reactions at multiple sites result in controlled exothermic reactions and improved efficiency.

[0214] Embodiments of the present invention provide activation of a polymerization catalyst at one or more depths in a matrix material. The catalyst may be present on the surface of the matrix material, at depths below the surface, or embedded within the matrix material. For example, the catalyst may be located below the surface at depths of approximately 0.01 μm, 0.01 μm to 0.05 μm, 0.05 μm to 0.1 μm, 0.1 μm to 0.2 μm, 0.2 μm to 0.3 μm, 0.3 μm to 0.4 μm, 0.4 μm to 0.5 μm, 0.5 μm to 0.6 μm, 0.6 μm to 0.7 μm, 0.7 μm to 0.8 μm, 0.8 μm to 0.9 μm, 0.9 μm to 1 μm, 1 μm to 5 μm, 5 μm to 10 μm, or greater than 10 μm, and any and all increments in between.

[0215] In one embodiment, the present invention relates to solid-state polymerization in which the molecular weight increases over time, in which the polymer is already in a solid or highly viscous state, but the polymerization yield or molecular weight can be increased, for example, in situ by incorporating matrix microparticles and processing with RF or MW.

[0216] Particle composition and structure Referring to Figures 5A and 5B, in some embodiments, the matrix particles of the present invention may have a wide variety of compositions. The matrix material may be deformable at will. In some embodiments, multiple matrices are used in one embodiment. In some embodiments, one or more susceptor components may be used. In some embodiments, one or more releaseable and / or activateable components are contained in or on the matrix. In some embodiments, one or more releaseable and / or activateable components include one or more catalysts, co-catalysts, co-reactants, fuels, explosives, other components, and mixtures thereof. In some embodiments, the releaseable and / or activateable components are released by one or more means, including, for example, dissolution, expansion, cracking, light, and / or one or more combinations thereof.

[0217] Variable matrix materials As used herein, “variable matrix” refers to a material that, when heated, can be deformed, dissolved, melted, burst, expand, contract, plasticized, and / or solvated in such a manner that it releases its active components, such as chemical contents. Matrix particles can have almost any geometric structure, shape, or size. For example, as shown in Figure 4, matrix particles can be formed into shapes including spheres, plates, ribbons, sheets, or coatings, rods, or porous structures including expanded fibers, such as foams, or one or more irregular or disjointed shapes.

[0218] In some embodiments shown in Figures 5A and 5B, 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 includes a mixture of isotropic and anisotropic structures.

[0219] The matrix material can consist of any suitable material as understood in the art. In some embodiments, the matrix material may be a monomer, oligomer, or polymer. For example, the matrix may contain methyl methacrylate. In some embodiments, the matrix material consists of polymer microparticles. For example, polymer microparticles may be made from polymethyl methacrylate (PMMA), styrene, and / or one or more polymers or copolymers thereof. The microparticles may also be blends, alloys, and mixtures of polymers.

[0220] Polymer microparticles may include polymer microspheres and microcapsules. Microcapsules may be porous or partially open.

[0221] In some embodiments, the microparticles are spherical microparticles. The microparticles can have an effective diameter of about 0.1 μm to about 1000 μm. As used herein, “effective diameter” refers to the diameter of equivalent spherical microparticles of the same volume or weight. For example, microparticles can have effective diameters of approximately 0.1 μm to approximately 0.5 μm, approximately 0.5 μm to approximately 1 μm, approximately 1 μm to approximately 5 μm, approximately 5 μm to approximately 10 μm, approximately 10 μm to approximately 50 μm, approximately 50 μm to approximately 100 μm, approximately 100 μm to approximately 200 μm, approximately 200 μm to approximately 300 μm, approximately 300 μm to approximately 400 μm, approximately 400 μm to approximately 500 μm, approximately 500 μm to approximately 600 μm, approximately 600 μm to approximately 700 μm, approximately 700 μm to approximately 800 μm, approximately 800 μm to approximately 900 μm, approximately 900 μm to approximately 1000 μm, and any and all increments in between.

[0222] In one embodiment, the effective diameter of a microparticle is one of the numbers measured in μm units, or one of the numbers within the range defined by any two of the following numbers in μm units, including the endpoints: 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.

[0223] In one embodiment, the microspheres referred to herein are microparticles composed of a homogeneous and solid polymer matrix material, while microcapsules are core-shell microparticles whose core may 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 may include pores formed on the surface, or external pores, and / or internal pores. The pores may be isolated or interconnected. The pores result in a matrix material with a very low mass density. The pores are suitable for encapsulating susceptors, as well as releaseable and / or activatable components such as activators, catalysts, co-catalysts, co-reactants, oxidizers, reaction inhibitors, accelerators, and / or one or more other releaseable components.

[0224] In some embodiments, the matrix material is composed of monodisperse polymer particles. In some embodiments, the matrix material is composed of polydisperse polymer particles. Polydisperse may include a narrow particle size dispersion, such as a unimodal, bimodal, or trimodal distribution. In some embodiments, polydisperse includes an intermediate particle size dispersion. In some embodiments, polydisperse includes a broad particle size dispersion. In some embodiments, the polydisperse includes particle sizes in the following ranges: approximately 1 nm to approximately 10 nm, approximately 10 nm to approximately 50 nm, approximately 50 nm to approximately 100 nm, approximately 100 nm to approximately 200 nm, approximately 200 nm to approximately 400 nm, approximately 400 nm to approximately 600 nm, approximately 600 nm to approximately 800 nm, approximately 800 nm to approximately 1000 nm, approximately 1 μm, approximately 1 μm to approximately 1.5 μm, approximately 1.5 μm to approximately 2 μm, approximately 2 μm to approximately 2.5 μm, approximately 2.5 μm to approximately 3 μm, approximately 3 μm to approximately 3.5 μm, approximately 3.5 μm to approximately 4 μm, approximately 4 μm to approximately 4.5 μm, approximately 4.5 μm to approximately 5 μm, and any and all increments between them. In some embodiments, the average particle size is approximately 0.1 μm at most. In some embodiments, the average particle size is approximately 0.1 μm to 0.5 μm, approximately 0.5 μm to 0.8 μm, approximately 0.8 μm to 1 μm, approximately 1 μm to 1.2 μm, approximately 1.2 μm to 1.5 μm, approximately 1.5 μm to 1.8 μm, approximately 1.8 μm to 2 μm, approximately 2 μm to 4 μm, approximately 4 μm to 6 μm, approximately 6 μm to 8 μm, approximately 8 μm to 10 μm, and approximately 1 The ranges are 0 μm to approximately 20 μm, approximately 20 μm to approximately 40 μm, approximately 40 μm to approximately 60 μm, approximately 60 μm to approximately 80 μm, approximately 80 μm to approximately 100 μm, approximately 100 μm to approximately 200 μm, approximately 200 μm to approximately 400 μm, approximately 400 μm to approximately 600 μm, approximately 600 μm to approximately 800 μm, approximately 800 μm to approximately 1000 μm, and any and all values ​​in between.

[0225] In some embodiments, the matrix material of the matrix particles has a molecular weight of up to 10 kDa. In some embodiments, the matrix material of the matrix particles has molecular weights 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 in between. Matrix materials with very high molecular weights, such as matrix materials of branched or crosslinked polymers such as rubber, are also within the scope of the present invention.

[0226] In some embodiments, the matrix material has a molecular weight provided by any number below in kDa units, or by any two numbers below in kDa units, within a range that includes the endpoint of such a range: 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, 10 000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, and 1000000.

[0227] In some embodiments, the polymer particle dispersion contains particles having a low level of crosslinking. In some embodiments, the polymer particle dispersion contains particles having a standard or intermediate level of crosslinking. In some embodiments, the polymer particle dispersion contains particles having a high level of crosslinking.

[0228] Susceptor In some embodiments, the matrix particle composition of the present disclosure includes one or more susceptors. A susceptor contemplated herein is a particle that can be heated or activated to generate heat. The susceptor is composed of a material that creates a higher heating rate or lower heat capacity than the surrounding or adjacent matrix material. The faster heating rate of the susceptor causes a change in the matrix, as previously defined, upon application of an energy source without heating the bulk of the matrix material. The heated susceptor can induce deformation of the matrix material, so that components or chemical constituents that can affect reactions, such as catalysts or inhibitors in 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 iron or non-ferrous metals, such as, 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.

[0229] Embodiments of iron susceptors include one or more ferrite powders, superparamagnetic iron oxide (SPION) particles, etc., and include one or more combinations thereof. Embodiments of susceptors include one or more of graphene, graphite oxide fullerene, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, filled or doped carbon nanotubes, carbon sheets, bucky paper, nanocrystalline cellulose, etc., and include one or more combinations thereof.

[0230] Embodiments of susceptors are composed of one or more materials that generate heat when exposed to high frequency (RF) radiation and / or microwave (MW) radiation, and microwave heating is used as an example for describing the process of the present invention below. Microwaves applied externally can generate internal matrix heating. Without being bound by theory, unlike conventional means of bulk heating, the microwave induction heating rate is not limited to the rate of heat transfer from an external heat source to the interior of the bulk reaction mixture. Therefore, microwave heating is more efficient than conventional heating. That is, microwave heating provides more rapid and uniform heating of the bulk reaction mixture having the matrix particles of the present invention dispersed therein. Further, while conventional heating occurs via heat flow from an external heat source, conventional heating propagates from the surface to the core of the bulk reaction mixture by one or more means including conduction and / or convection, and through mixing.

[0231] Therefore, the surface of the bulk reaction mixture often 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 heats the immediate vicinity of the bulk reaction mixture and the temperature gradually decreases towards the core. Even when an equilibrium temperature is established, the walls of the bulk reaction mixture proximate to the reaction vessel are likely to have much higher temperatures from higher temperatures, introducing non-uniform yields and chemical properties of the bulk reaction mixture proceeding towards the final product. For example, in a polymerization reaction, a bulk reaction mixture starting from monomers and oligomers will either have a certain distribution of molecular weights from the outside to the core of the bulk reaction mixture if temperature-dependent, or have higher decomposition closer to the reaction vessel, or have higher gelation / cross-linking at the reaction vessel walls.

[0232] This can lead to uneven heating, overheating, and / or underheating, resulting in reaction non-uniformity, which can then affect the yield or create problems with other reaction parameters. However, microwave heating can be performed uniformly, whether on the core or outside of the bulk reactant, because microwaves penetrate the matrix material and thermally activate or excite the susceptors in the core of the bulk material almost simultaneously, thus generating heat inside the bulk material and allowing the core of the matrix to remain at a higher temperature than the surface in general. In other words, it is possible to generate a localized heat source of very small size.

[0233] Therefore, in some embodiments, the susceptor is located within the core of a matrix particle, such as a polymer matrix material, so when microwaves are applied in this manner, the susceptor is heated, resulting in heating of the core of the matrix particle. In some embodiments, the susceptor is located on the surface of the matrix particle, so when microwaves are applied, localized rapid heating of the surface of the matrix particle occurs.

[0234] Embodiments of the susceptor can be activated at one or more frequencies or frequency ranges. Examples of frequencies include one or more within the following ranges: up to approximately 100 MHz, approximately 100 MHz to approximately 200 MHz, approximately 200 MHz to approximately 400 MHz, approximately 400 MHz to approximately 600 MHz, approximately 600 MHz to approximately 800 MHz, approximately 800 MHz to approximately 1000 MHz, approximately 1000 MHz to approximately 1500 MHz, approximately 1500 MHz to approximately 2000 MHz, approximately 2000 MHz to approximately 2500 MHz, approximately 2500 MHz to approximately 5000 MHz, approximately 5000 MHz to approximately 7500 MHz, and any and all increments between them. A preferred frequency range is 900 MHz to 2500 MHz.

[0235] In some embodiments, the frequency, measured in MHz, is one of the following numbers, or is within a range defined by any two of the following numbers, including the endpoint of such a range in MHz: 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.

[0236] Embodiments of the susceptor include one or more shapes. For example, the susceptor may be spherical, cylindrical, disc-shaped, tubular, or cubic, and may have one or more other regular polygonal prism shapes, one or more irregular shapes, and / or one or more combinations thereof.

[0237] In some embodiments, the susceptor is functionalized. In some embodiments, the susceptor includes both functionalized and unfunctionalized susceptors. In some embodiments, the functional groups include surface functional groups, and the functional groups are added by one or more monomer or polymer surfactants. For example, in some embodiments, the susceptor may include one or more carboxyl groups, hydroxyl groups, methyl groups, etc. The susceptor may include one or more functional groups that increase or decrease hydrophilicity or hydrophobicity. The susceptor may include different functional groups such that one region of the susceptor is more hydrophilic or hydrophobic than another region of the susceptor. For example, the susceptor may have functional groups such that the susceptor has polar and nonpolar ends.

[0238] Releaseable and / or activatable components In some embodiments, the matrix material includes one or more releaseable and / or activatable components, also known as releaseable components or active components. One or more releaseable and / or activatable components may be encapsulated or contained within the matrix material, which may be a polymer, oligomer, monomer, or a mixture of these three. For example, one or more releaseable components may be physically contained or encapsulated within one or more pores in a microparticle matrix material. In some embodiments, one or more releaseable components may be chemically contained within a polymer matrix material; that is, one or more releaseable components may be chemically bonded to one or more materials of the matrix within the matrix particles. The releaseable components may include one or more catalysts, co-catalysts, co-reactants, oxidizers, reaction inhibitors, chelating agents, initiators, accelerators, surfactants, modifiers, fuels, explosives, and / or combinations thereof. The releaseable components may include any chemical, organic, or inorganic chemical combinations as understood in the art. In some embodiments, one or more releaseable components may include one or more compounds capable of initiating polymerization, such as anionic polymerization, cationic polymerization, or free radical polymerization.

[0239] In some embodiments, one or more releaseable components include one or more components that initiate one or more reactions, including redox reactions such as those in anaerobic adhesion. For example, one or more releaseable components may include one or more hydroperoxides and one or more transition metals. One or more releaseable components may be contained in different microcapsules within the matrix, in different pores, encapsulated within the matrix material, bound to one or more components of the matrix material, or maintained separately and only in contact when the matrix material is heated or activated.

[0240] In one embodiment, the one or more releaseable components include one or more metal accelerators or catalysts, such as ferrocene or other metallocenes. The one or more catalysts can be combined with peroxides and / or other compounds to activate or deactivate polymerization. In some embodiments, catalysts include one or more of Cu-acetylacetonate, Cu-2-ethylhexanoate, ferrocene, dimethylaminomethylferrocene, and / or combinations thereof. In some embodiments, the one or more releaseable components include one or more free radical stabilizers, such as hydroquinone or p-methoxyphenol.

[0241] For example, in some embodiments comprising compositions containing anionic cyanoacrylate and / or methylene malonate, one or more releaseable components may include one or more inorganic or organic bases (e.g., sodium propionate). In yet another example, in the cationic polymerization of epoxy resins, one or more components such as diaryliodonium and triarylsulfonium, blocked superacids, and cationic catalysts are released. In some embodiments such as condensation polymerization, one or more releaseable components may include one or more catalysts such as antimony, germanium, titanium, and aluminum compounds.

[0242] Fuels and explosives are another example of materials that can be used in this way. Specifically, fuels or other explosive materials can be used individually or in combination, with or without the additional materials described, to initiate chemical reactions and release large amounts of energy in various forms, either individually or in combination with other reactive materials, to accelerate events ranging from the driving of pistons in an engine to explosive devices, ignition events, and simple rapid heating events.

[0243] In one embodiment, the releaseable component can modify the physical properties of the bulk reaction mixture, for example, by increasing or decreasing its viscosity, or, in particular, by providing the bulk reaction mixture with color or other optical properties when the product reaches its chemical equilibrium.

[0244] It should be noted that carbon nanostructures act simultaneously as susceptors and / or releaseable components. In other words, in one embodiment, the carbon nanostructure exists only as a susceptor. In another embodiment of the present invention, the nanostructure exists as a releaseable and / or activatable component. In yet another embodiment, the carbon nanostructure exists and functions as both a susceptor and a releaseable and / or activatable component. Embodiments of the releaseable agent include one or more of graphene, fullerene, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, filled or doped carbon nanotubes, carbon sheets, buckypaper, etc., and one or more combinations thereof. In one embodiment, the releaseable component is a carbon nanotube releaseably attached to a core, shell, deformable material, force-modifying material, or matrix material of a matrix particle. In another embodiment, the number of carbon nanotubes attached to a given position in a cluster inside a matrix particle is 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0245] particle structure Embodiments of this disclosure provide a matrix particle composition having a matrix material comprising one or more particles as described herein, one or more susceptors as described herein, and / or one or more releaseable components as described herein. The matrix particle composition may simply be structured as a matrix material containing the susceptors and releaseable components and may exist in any geometric configuration required by application. For example, the matrix particles may exist in a spherical or substantially spherical configuration, a ribbon or sheet-like configuration, a rod-like or fibrous 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 releaseable components may not be physically released but rather may be chemically activated to perform their function.

[0246] In some embodiments, the matrix particle composition may have various phases containing either a susceptor and / or an activatable and / or releaseable component. In some embodiments, the matrix particle composition may have a continuous phase containing both a susceptor and / or a releaseable component. In some embodiments, one or more susceptors, or releaseable components such as activators / catalysts, may be contained in a first layer of the matrix material of the matrix particle composition and / or one or more subsequent or alternating coating layers.

[0247] In some embodiments, the particle composition includes one or more regions containing hydrophilic chemicals, hydrophobic chemicals, and / or hydrophilic and / or hydrophobic chemicals. In some embodiments, one or more functionalized susceptors are positioned in or on the particle composition such that similarly charged susceptor functional groups and particle chemicals are aligned. For example, the hydrophilic regions of one or more susceptors align with one or more regions of the matrix particle composition having one or more hydrophilic chemicals. Similarly, in some embodiments, the hydrophobic regions of one or more susceptors align with one or more regions of the matrix particle composition having one or more hydrophobic chemicals. Thus, the position of one or more susceptors in or on the matrix particle composition may be oriented by the hydrophilic or hydrophobic regions of the matrix particle composition.

[0248] Embodiments of a matrix particle composition include configurations in which a susceptor is combined with one or more of a matrix material and a releaseable component. Embodiments of a matrix particle composition include configurations in which a susceptor can 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 layer of the matrix material and one or more additional adjacent layers of the matrix material. For example, in some embodiments, the matrix particle composition may include a single matrix material or matrix material layer, two matrix material layers, three matrix material layers, and so on. The matrix particle composition may include one or more homogeneous layers, one or more heterogeneous layers, and / or a combination thereof. For example, in some embodiments, two or more susceptors or types of susceptors are included in a single matrix particle composition. Additional susceptors may be located on the same matrix material layer, adjacent matrix material layers, alternating matrix material layers, and so on.

[0249] In some embodiments, two or more releasable components, such as an active agent or a catalyst, are included in the same matrix material layer or different matrix material layers. The active agent or catalyst can be located in the same matrix material layer, adjacent matrix material layers, alternating matrix material layers, etc. In some embodiments, two or more releasable components are included in the same matrix material layer or different matrix material layers. The releasable components can be located in the same matrix material layer, adjacent matrix material layers, alternating matrix material layers, etc.

[0250] In some embodiments, each matrix material layer includes one combination of a susceptor, an active agent / catalyst, and a releasable component such as an active agent / catalyst. In some embodiments, each matrix material layer includes two or more combinations of a susceptor and a releasable component such as an active agent / catalyst. In some embodiments, the matrix particle composition includes two or more matrix material layers, and each matrix material layer includes the same combination of a susceptor and a releasable component such as an active agent / catalyst. In some embodiments, the particle composition includes two or more matrix material layers, and each matrix material layer includes a different combination of a susceptor and a releasable component such as an active agent / catalyst.

[0251] In some embodiments, the matrix particle composition includes two or more matrix material layers, and each layer is formulated to have a curing time within the same time interval. In some embodiments, the matrix particle composition includes two or more matrix material layers, and each layer is formulated to have a curing time at varying time intervals, such as in a shaped structure. In some embodiments, the layered matrix material is ordered to manage stress and / or other physical properties in the particle composition or in the material to which they are applied therein or thereon. For example, in some embodiments, the particle composition is formulated with different amounts or concentrations of one or more activatable matrix components, active agents, catalysts, releasable components, etc.

[0252] For example, the matrix particles may be optionally supported and / or protected, in whole or in part, by a shatterable or non-shatterable support, such as a metal, ceramic, or glass, and by a three-dimensional solid object, such as a foam, that is coated with or impregnated with the matrix particle composition. In a further example, the object may have a rough texture, a protruding texture, or a similar surface texture, for example, hidden beneath the structure, in order to prevent shattering by the surrounding matrix material. Another example is the matrix particle composition, which may include coated beads, particles, granules, etc., including metallic glass beads, or even susceptors as beads for melting or deforming the matrix particle composition coated on the surface through heating.

[0253] In some embodiments, for example, multiple matrices are used if required by a particular application. The matrices can be formed in various configurations, including one or more coated layers, patterned films or layers, textured shapes, and so on.

[0254] In all applications, the susceptor is excited via external high-frequency electromagnetic radiation (EMR) to partially or completely alter one or more surrounding matrices, for example, by deforming, dissolving, or melting them, thereby releasing catalysts, co-catalysts, inhibitors, co-reactants, or accelerators, fuels, explosives, or other components. In some embodiments, the susceptor, such as a carbon nanotube (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.

[0255] Matrix particles provide an efficient method for delivering susceptors into formulations used, for example, in adhesives, coatings, composites, molding applications, and polymer systems. The use of matrix particles as a carrier helps maintain rheological characteristics; for example, even at low filler levels, CNTs cause a sharp increase in viscosity, creating processing challenges.

[0256] Furthermore, various susceptors are used depending on the specific application. For example, in the curing of opaque polymers, single-wall and multi-wall carbon nanotubes, sheets, and fiber susceptors generally provide highly efficient energy susceptor materials for heating and releasing a given catalyst. In another example where optical transparency is the driving factor, boron nitride-containing CNTs may be used for transparency.

[0257] The size of the susceptor components ranges from nanometers to micrometers to millimeters. For example, in some embodiments, the size of the susceptor components ranges from about 1 nm to 10 nm, about 10 nm to about 100 nm, about 100 nm to about 1 μm, about 1 μm to about 10 μm, about 10 μm to about 100 μm, about 100 μm to about 1000 μm, and any and all increments in between.

[0258] In some embodiments, the size of the susceptor component is one of the following numbers measured in nm, or within a range defined by any two of the following numbers including the endpoint of such a range in nm, or the sum of any two of the following numbers in nm: 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.

[0259] In some embodiments, the susceptors are uniformly dispersed in the matrix material. The dispersion of the susceptors can allow for the use of optimized weights of the susceptors. In some embodiments, well-dispersed susceptors can generate strong van der Waals forces between the susceptors and the matrix material, which can be theorized, although we do not wish to be bound by any theory as limiting the scope of the invention. The interaction between the susceptors and the matrix can also occur through both covalent and non-covalent bonds.

[0260] Possible susceptor components include carbon nanotubes, carbon nanostructures, and iron particles containing superparamagnetic iron oxide nanoparticles (SPION).

[0261] Catalysts, co-catalysts, inhibitors, co-reactants, accelerators, fuels, explosives, other components, and mixtures can be of substantially any composition, but preferably the final particles are present at a concentration suitable for the required chemical reaction. Applications are highly unique, and their requirements can vary considerably.

[0262] In some embodiments, the concentration of susceptor components can generally vary from 0.01% to as much as 10%, depending on the application itself and its requirements, and the final decision-maker. Energy requirements are derived from the deformation temperature and mechanics, heat transfer to the surrounding matrix, and the time frame of events ranging from one-thousandth of a second to several tens of seconds or more. In some embodiments, the matrix comprises one or more waxes. Examples of waxes include one or more natural waxes such as carnauba wax. Examples of waxes include one or more synthetic waxes such as polyethylene wax. The wax can be a combination of both synthetic and natural waxes, and the combination has a distinct melting point. In some embodiments, the wax has a melting temperature and / or deformation temperature in the range of about 50°C to 300°C. For example, the wax matrix in some embodiments has melting temperatures of approximately 50°C to approximately 75°C, approximately 75°C to approximately 100°C, approximately 100°C to approximately 125°C, approximately 125°C to approximately 150°C, approximately 150°C to approximately 175°C, approximately 175°C to approximately 200°C, approximately 200°C to approximately 225°C, approximately 225°C to approximately 250°C, approximately 250°C to approximately 275°C, approximately 275°C to approximately 300°C, and any and all increments in between.

[0263] Wax as a matrix material "Wax" means any naturally occurring or synthetically occurring wax. It also includes blends or mixtures of one or more naturally occurring and / or synthetically occurring waxes. Naturally occurring waxes include plant waxes, animal waxes, and mineral waxes. Synthetic waxes are produced by physical or chemical processes. Naturally occurring waxes are mixtures and therefore softer and melt at lower temperatures than their pure components.

[0264] The wax is of general formula C n H 2n+2It can be a paraffin wax that is a linear alkane having the following properties, where n varies from 13 to 80. The paraffin wax defined by n=13 is called tridecane, and the one with n=80 is called octacontane. 13 The melting point of wax is -5.4°C. Similarly, the melting point of C60 wax is 100°C. Similarly, the melting points of high molecular weight waxes (C60-C80) are higher than 100°C. Depending on the temperature range over which the bulk reaction mixture needs to be heated, wax-based matrix particles can be prepared that contain specific wax cores that change, deform, or melt within that particular temperature range.

[0265] Examples of plant-based waxes include mixtures of non-esterified hydrocarbons, which may be more abundant than esters. Plant cuticle waxes are mixtures of substituted long-chain aliphatic hydrocarbons, containing alkanes, alkyl esters, sterol esters, fatty acids, primary and secondary alcohols, diols, ketones, aldehydes, aliphatic aldehydes, primary and secondary alcohols, β-diketones, triacylglycerols, and more. Specific examples of plant waxes include carnauba wax, candelilla wax, ouricury wax, jojoba wax, bayberry wax, Japan wax, sunflower wax, tall oil, beef tallow wax, rice wax, and beef tallow.

[0266] Animal waxes include beeswax and waxes secreted by other insects. The main component of beeswax used to construct honeycomb is myricyl palmitate, an ester of triacontanol and palmitic acid. Whaleswax is found in large quantities in the head oil of sperm whales. One of its main components is cetyl palmitate, another ester of fatty acids and fatty alcohols. Lanolin is a wax obtained from wool, consisting of sterol esters. Other examples of animal waxes include lanocerin, shellac, and ozokerite.

[0267] Examples of mineral waxes include montane wax, paraffin wax, microcrystalline wax, and intermediate waxes. Many natural waxes contain esters, but paraffin wax is a hydrocarbon, usually a mixture of alkanes of the same group. Paraffin wax is a mixture of saturated n- and iso-alkanes, naphthenes, and alkyl and naphthene-substituted aromatic compounds. The degree of branching has a significant effect on its properties. Montane wax is a fossil wax extracted from coal and lignite. It is very hard and reflects a high concentration of saturated fatty acids / esters and alcohols. Montane wax contains chemical components formed from long-chain alkyl acids and alkyl esters with a chain length of about 24-30 carbon atoms. In addition, natural montane is not a "pure" wax as it contains resin acids, polyterpenes, and some alcohols, ketones, and other hydrocarbons. Montane is a saponifiable wax with a saponification value of about 92 and a melting point of about 80°C. In addition to montane wax, other naturally derived waxes are known to be used in various industries, including petroleum waxes derived from processed crude oil. Petroleum waxes include macrocrystalline waxes, microcrystalline waxes, petrolatum, and paraffin wax. Paraffin wax is also a natural wax derived from petroleum and is mainly composed of straight-chain alkanes with an average chain length of 20 to 30 carbon atoms.

[0268] Examples of 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. Some waxes are obtained by cracking polyethylene at 400°C. The product is of the formula: (CH2) n It contains H2, and in the formula, n is in the range of approximately 50 to 100.

[0269] Furthermore, synthetic polyethylene waxes with low molecular weights, i.e., molecular weights of less than approximately 10,000, and synthetic waxes containing polyethylene with wax-like properties are also known. Such waxes can be formed by directly polymerizing ethylene under conditions suitable for controlling molecular weight. Polyethylene with molecular weights in the range of approximately 2,000 to 4,000 is a wax, and in the range of approximately 4,000 to 12,000, it becomes a wax resin.

[0270] Fischer-Tropsch waxes are polymethylene waxes produced by a specific polymerization synthesis, specifically the Fischer-Tropsch synthesis (polymerizing carbon monoxide under high pressure, high temperature, and a special catalyst to produce hydrocarbons, followed by distillation to separate the product into liquid fuel and wax). Such waxes (microcrystalline, polyethylene, and polymethylene type hydrocarbon waxes) can be chemically modified, for example, by air oxidation (giving an acid value of 30 or less and a saponification value of 25 or more), or by modification with maleic anhydride or carboxylic acids. Such modified waxes can be more readily emulsified, saponified, or esterified in water. Other known synthetic waxes are polymerized alpha-olefins. These are waxes formed from high molecular weight alpha-olefins with 20 or more carbon atoms that have wax-like properties. This substance is highly branched, has a broad molecular weight distribution, a melting point in the range of about 54°C to 75°C, and a molecular weight of about 2,600 to 2,800. Therefore, waxes differ depending on the properties of the base material, as well as the polymerization or synthesis process, and the use and type of any chemical modifications, resulting in different chemical structures.

[0271] Matrix particles can be produced by any of the following processes: polymerization or physical material decomposition, emulsification, dispersion, and / or suspension polymerization, core-shell polymerization, solvent dispersion, cavitation of fluids and / or solids in fluids, fusion of susceptors and catalysts, grinding after fusion, etc.

[0272] As shown in Figure 1, solid matrix particles containing carbon nanotubes as susceptor components and a catalyst to facilitate the chemical reaction are shown. High-frequency waves are impacted onto the matrix particles, thereby heating the carbon nanotube particles. These particles are embedded in close proximity to the catalyst particles. The matrix material melts or deforms completely or partially, but as a result of the high-frequency waves, the catalyst is released, which then catalyzes the reaction of the material into which the multiple matrix particles are incorporated.

[0273] In this embodiment, RF or MW energy merely heats and melts the matrix particles. The heating rate of the matrix particles is several orders of magnitude higher than that of the adjacent material. Differential heating of the matrix particles leads to deformation of the matrix particles without causing bulk heating. Furthermore, the uniformly dispersed matrix particles and their size do not result in any noticeable heating of the adjacent formulation. As a result, RF or MW energy activates the release of the matrix particle contents, inducing uniform and rapid polymerization. In one embodiment, less than 2% of the catalyst is required, typically in the ppm range. In one embodiment, the catalyst percentage is any number selected from the numbers provided below, or within the range defined by any two of the numbers below, including the endpoint of such a range: 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.

[0274] Figure 2 shows a reaction injection molding process currently being implemented according to the present invention. As a result of the present invention, complex mixing is not required. RF curing is performed instead of thermal curing. This eliminates or reduces the use of steel molds, and the reaction can be achieved under lower pressure without applying overall heating, making it faster. It also significantly reduces curing time.

[0275] As shown in Figure 3, as is currently practiced, multiple film lines are used for multiple layers as a film lamination adhesive. By using the present invention, one line can be used for multiple layers. The advantages are that it is fast, heat-free, can cure opaque materials, and has no depth limitations. In addition to precise control when curing is performed during production, control of the curing location is also achieved.

[0276] In one embodiment, RF or MW is a directional source in that the radiation is focused on a specific object or region of interest.

[0277] In some embodiments, the matrix may 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.

[0278] In some embodiments, the coating adheres to the matrix by one or more means, including, for example, entanglement, van der Waals interactions, or through one or more chemically bonded compounds. In some embodiments, the coating comprises one or more waxes, one or more hydrophobic compounds and / or hydrophobic functional groups, one or more oils, fatty acids, and one or more compounds having nonpolar components including a nonpolar tail.

[0279] The coating may have thicknesses of up to 10 nm, approximately 10 nm to 15 nm, approximately 50 nm to 100 nm, approximately 100 nm to 500 nm, approximately 500 nm to 1 μm, approximately 1 μm to 2 μm, approximately 2 μm to 5 μm, approximately 5 μm to 10 μm, approximately 10 μm to 50 μm, approximately 50 μm to 100 μm, approximately 100 μm to 500 μm, approximately 500 μm to 1 mm, approximately 1 mm to 2 mm, approximately 2 mm to 5 mm, approximately 5 mm to 10 mm, approximately 10 mm to 50 mm, approximately 50 mm to 100 mm, approximately 100 mm to 500 mm, and any and all increments in between.

[0280] Embodiments of the matrix may include one or more additional components to provide controlled, demand-responsive release. For example, the matrix, and / or coatings and / or discontinuous coatings containing the matrix, may be coated on or not coated on any surface where matrix activation is easily facilitated, such as circular fibers, woven fibers, polymer fibers, hollow fibers, reinforcing fibers used in composites, sheets, flexible or nonflexible materials, foams and other porous structures, nonwoven materials, woven materials, polymer scrims, and reinforcing scrims.

[0281] In some embodiments, the matrix includes one or more fillers. Embodiments of fillers include particles such as fibers. Fibers may have one or more lengths. Fibers may include crushed fibers. Embodiments of fillers include one or more of the following: clay, aggregate, plasticizer, plastic particles, nanoparticles of different shapes, etc.

[0282] Particle activation process and apparatus Particle activation processes and apparatus constitute a complete "system" including various types of susceptors, activators, matrix components, RF and / or MW energy sources, material handling, software, and control.

[0283] Velocity, time, unit throughput, shape elements, topology, and unit volume are among the dependent features that are analyzed for each application and adjusted by the system to produce the desired final artifact or result for a given set of materials.

[0284] Susceptors are excited via external high-frequency EMR, partially or completely deforming the surrounding matrix and releasing catalysts, co-catalysts, co-reactants, or accelerators. In fields such as the remote Joule heating properties of CNTs, heated CNTs are used to deform the surrounding matrix, although they are not bound by the theory of the physical properties of how CNTs heat the surrounding material.

[0285] In its most common form, microwave electromagnetic radiation having wavelengths in the range of approximately 1 meter to 1 millimeter, with frequencies of 300 MHz (1 m) to 300 GHz (1 mm), is used to excite a susceptor and deform the surrounding matrix to release a catalytic or activating material. In practice, a variety of electromagnetic wavelengths and frequencies can be used, and preferably, the most common today for consumer and industrial applications, are frequencies of 915 MHz and 2450 MHz. However, one or more suitable frequencies may include up to approximately 100 MHz, approximately 100 MHz to approximately 200 MHz, approximately 200 MHz to approximately 400 MHz, approximately 400 MHz to approximately 600 MHz, approximately 600 MHz to approximately 800 MHz, approximately 800 MHz to approximately 1 GHz, approximately 1 GHz to approximately 1.5 GHz, approximately 1.5 GHz to approximately 2 GHz, approximately 2 GHz to approximately 2.5 GHz, approximately 2.5 GHz to approximately 5 GHz, approximately 5 GHz to approximately 7.5 GHz, and any and all increments in between.

[0286] [Table 1]

[0287] In one embodiment of the present invention, the process of applying electromagnetic radiation, i.e., impacting a bulk reaction mixture, is carried out for 10 seconds to 60 minutes. In another embodiment, the irradiation time is a number within a range defined by any one number selected from the following, or any two of the following, in seconds, including the endpoint of such range in seconds: 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.

[0288] In one embodiment of the present invention, EMR is used as a beam to collide with a bulk reaction mixture, and the bulk reaction mixture is exposed to RF or MW radiation.

[0289] Purpose Examples of applications, though not limited to these, include the following: Adhesive bonding When overall heating, multi-component mixing, long polymerization times, and / or depth are limited, such as by light and / or surface primer activation systems, the release of catalysts, co-catalysts, and / or accelerators as needed can be eliminated by dispersing the components as desired within the polymerizable composition and activating them as needed at a desired moment during bonding or / or component preparation processes. The advantages also include much more precise positioning without reactions that alter viscodynamics.

[0290] coating When overall heating, multi-component mixing, long polymerization times, and / or depth are limited, such as by light and / or surface primer activation systems, the release of catalysts, co-catalysts, and / or accelerators as needed can be eliminated by dispersing the components as desired within the polymerizable composition and activating them as needed at the desired moment in the coating, or coating and / or part preparation process. Advantages also include flow control before and without reactions that alter viscodynamics. Limitations of UV-curable systems, such as incomplete curing in shaded areas and parts with complex shapes, can be overcome. Curing of 3D and concave parts with large appendages is unrestricted. Coating speeds can be matched upstream and downstream processing, eliminating obstacles to manufacturing throughput.

[0291] Molded and Composite Materials When overall heating, multi-component mixing, long polymerization times, and / or depth are limited, such as by light and / or surface primer activation systems, the release of catalysts, co-catalysts, and / or accelerators as required can be eliminated by dispersing the components as desired within the polymerizable composition and activating them as required at a desired moment in the molding or molding and / or part preparation process. Parts can be filled with many materials. Parts may be the same size as or larger than 14 feet x 14 feet in cross-section. In the context of this description, all publications, patent applications, patents, and other references referred to herein are expressly incorporated herein by reference in their entirety for all purposes, as if they were described in their entirety, unless otherwise indicated.

[0292] Surprisingly, nanoparticles and microparticles have been found to function as carriers for more effectively delivering nanomaterials to sealants, coatings, composites, adhesives, and other polymer products. Particularly interesting is when the physical properties of the final composition and / or physical product are achieved, including, but not limited to, thermal and electrical conductivity, improved and / or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy decay, and improved or controlled product life and / or failure.

[0293] The present invention specifically relates to particles that support, are filled with, or otherwise support layers of nanomaterials, including, but not limited to, metals and their chemical products, graphene, nanotubes and similar structures, in order to minimize the need for a more significant amount of such nanomaterial, for example, to benefit from improved physical, electrical, conductive and other similar properties.

[0294] Optionally, crosslinking chemistry can be incorporated into or on the surface of the particles, either simply using surface chemistry, or as a ligand or oligomer-like structure that can even further enhance the physical properties described.

[0295] Specifically, structures such as nanotubes, specifically nanomaterials such as carbon nanotubes and / or graphene, can be incorporated into polymer particles, and / or polymer particles can be coated with nanomaterials. This basic concept helps, among other things, limit the overall amount of material required, can provide a large surface area containing the structure in which separating forces are dispersed, and can limit aggregation, etc. When nanoparticles and / or microparticles are coated with coatings that improve van der Waals forces and other physical or chemical forces, these effects can be further improved and / or amplified and controlled, if desired.

[0296] The literature describes, for example, the coating of such particles with carbon nanotubes or the coating of individual nanotubes. Here, we differentiate by coating the particles with nanotubes and then coating them with a force-improving composition, incorporating two or more, preferably three or more nanotubes and / or coating them with the force-improving composition.

[0297] Optionally, any chemical functional groups for subsequent reactions or physical effects can be incorporated into the particles and / or their coatings. Examples of chemical reactions are numerous and not limited to crosslinking and / or polymerization reactions. Physical effects include, for example, ligand, polymer, or oligomer structures by physical combination with a surrounding polymer matrix, or, in the case of metal or soap-like ligands, by dispersion or inclusion in emulsions, dispersions, etc., in solvents, water, or other substances. Optional inclusion of catalysts, co-catalysts, accelerators, fuels, energy materials, etc.—incorporated by reference as fully described herein, see U.S. Patent Application No. 18 / 055,302 by Malofsky et al.

[0298] An additional object of the present invention is to provide polymer nanoparticles and microparticles having functional groups on their surface that can be irreversibly / reversibly reduced when a composition containing polymer microparticles is applied to a composition containing sealants, composites, adhesives, other polymer products, etc.

[0299] Another objective is to provide functional groups capable of hydrogen bonding or non-covalent bonding such as van der Waals when compositions containing polymer microparticles are applied to compositions for sealants, composites, adhesives, and other polymer products.

[0300] Generally, these functional nanoparticles and microparticles are versatile platforms with tunable properties that can be adjusted to meet specific application requirements. These functional nanoparticles and microparticles are used in a wide range of applications, including adhesives, composites, laminates, sealants, coatings, inks, and plastics, in numerous end products across many consumer, industrial, and / or medical applications.

[0301] Functional nanomicroparticles include, but are not limited to, latex particles, nano and microgel particles, and colloidal particles composed of polymer chains dispersed in water or other solvents. They also include microgel particles that can swell or contract in response to changes in the environment.

[0302] Functional microparticles containing reactive functional groups such as carboxylic acids, amino groups, thiols, epoxy, acrylic, and isocyanates can be crosslinked with other functional particles.

[0303] In coatings, crosslinked polymer microparticles are used to produce compositions containing a high solid content and / or to improve rheological properties.

[0304] Polymers containing functional microparticles, such as water-based polyurethanes (WPU), polyester dispersions (PEDs), and polyacrylate emulsions (PAEs), are commonly used in wood coatings, metal coatings, printing inks, architectural coatings, and plastic coatings. Despite their inherent advantages, polymers have several drawbacks, including low mechanical strength, low hardness, high water sensitivity, and thermal softening. Water-based reactions are relatively slow and can also cause health problems due to the release and use of hydrazine, formaldehyde, and other toxic chemicals.

[0305] In addition to creating polymer particles that can be dispersed in liquids, surface functional groups eliminate the need for slow reactivity and the use of toxic chemicals to accelerate the reaction.

[0306] In the core-shell configuration, the nanomaterials present in the core and the crosslinking functional groups on the shell help protect the CNTs until secondary processing is performed. The released nanomaterials increase interaction and crosslinking density due to van der Waals forces.

[0307] In another aspect of the present invention, the present invention provides a microparticle composition comprising a nanomaterial in the core, a catalyst, a crosslinking agent, and functional groups on the shell. Further objects of the present invention can be achieved by generating microparticles having particle sizes in the range of 0.01 to 10 microns, and by modifying existing microparticles.

[0308] A further object of the present invention can be achieved by generating nanoparticles and microparticles having particle sizes in the range of 0.01 to 100 microns, including modifying existing microparticles.

[0309] The polymer microparticles of the present invention are manipulated to specific shapes, sizes, and surface chemistry so that hybrids of organic and inorganic materials can be created.

[0310] A further aspect of the present invention provides a method for producing crosslinked polymer microparticles in which nanomaterials are embedded. The crosslinked microparticles can be delivered in a masterbatch or as standalone particles.

[0311] Covalently adaptable networks (CANs) are polymer materials that have covalent bonds that can be broken and reformed under certain conditions. Materials with reversible or tunable properties such as mechanical strength or viscosity can be developed in this manner.

[0312] The low entropy of the functional groups on the microparticles improves the chances of CAN formation compared to conventional crosslinking agents. Carbon nanotubes and graphene on the surface of the functional microparticles provide additional adhesion sites for CAN formation.

[0313] These crosslinkable, reversible groups attached to microparticles help create self-healing coatings, adhesives, composites, and structural materials via CAN.

[0314] The functional groups (pressure-sensitive adhesives) on the microparticles used in PSAs improve their tackiness and allow them to adhere easily to surfaces. Functional microparticles provide additional contact points between the adhesive and the substrate, reducing the possibility of creep failure over time.

[0315] The addition of nanomaterials with high elastic modulus, such as CNTs and graphene, improves resistance to deformation.

[0316] Pressure causes the functional particles to break down in the PSA, releasing chemicals that promote further crosslinking with the substrate and improve adhesion. Functional microparticles provide an adjustable bond line thickness. Microparticles can, for example, increase the viscosity of the adhesive, which improves its shear strength and prevents it from flowing.

[0317] Further aspects of the present invention relate to superior thermal and electrical conductivity by incorporating materials with lower viscosity by using materials more efficiently and creating an apparent honeycomb network that enables the final polymer-based high-conductivity product.

[0318] The ability to heat a composition and, as required and with low to insignificant additional energy input, release catalysts, co-catalysts, accelerators, or other reaction-initiating compounds enables novel processes, materials, and subsequent products and processes that were previously unattainable, specifically with respect to hot-melt adhesives, molding, preforms, plastics for thermoplastic molding, and overmolding of dissimilar materials. In the overmolding process, the adhesive layer functions to enable compatibility between thermoplastic and thermosetting properties.

[0319] Specifically, the present invention relates to carbonaceous susceptor particles coated with a material capable of preventing strong van der Waals force interactions, and / or the addition of individual carbonaceous susceptors or clusters of carbonaceous susceptors coated with a material capable of preventing van der Waals interactions, so as to significantly minimize or eliminate the effects of van der Waals forces, and in particular enable the easy addition of the material at high concentrations, thereby facilitating RF heating and causing easy physical deformation, including softening or melting. The aforementioned coating significantly reduces aggregation or other macrostructures that can cause a significant increase in viscosity or similar physical effects. The coating can slow down, stop, or prevent thermal, electrical, or other similar effects where desired. The aforementioned compositions can be easily mixed with existing formulations using conventional equipment.

[0320] The applications of hot melt adhesives illustrate the overall possible effects, which can be extended to other products containing materials ranging from low molecular weight materials and bio-derived temperature-sensitive renewable materials to high molecular weight thermoplastic resins and polymers.

[0321] Specifically, the van der Waals effect is minimized, viscosity is significantly reduced throughout the temperature range, and it becomes possible to incorporate more of the coated material, so that carbonaceous materials can be coated as individual, cluster, coated particles, and optionally, other combinations incorporating other materials.

[0322] In one embodiment, the present invention facilitates RF heating, particularly microwave heating, to enable higher filling of the material in order to promote ease of processing and / or a high level of reinforcement. As described in the background art above, other objectives may include thermal or electrical conductivity, reaction initiation, CTE matching, thermal conductivity through particles, and the like.

[0323] The preform, in any of the properties described above, or in a selection of reactive materials using particles containing catalysts such as those described in Malofsky et al. U.S. Patent Application No. 18 / 055,302, includes another exemplary group of applications that allow the carbonaceous material to be initially added to a polymer in a molten material to initiate a reaction in which the particles maintain their integrity at the formation or deformation temperature during part fabrication processing until RF heating is performed to a higher temperature for release or exposure by catalyst or other means and subsequent activation. RF heating enables rapid manufacturing for high throughput and lower cost. Such a process in certain applications may eliminate the need for cooling of the B-stage preform or material.

[0324] The layers for plastic injection molding, blow molding, and thermal bonding (extrusion) of polymer or polymer-coated layers functioned similarly to those described above.

[0325] The advantages of additional reinforcing materials such as carbon, glass, aramid, ultra-high molecular weight polyethylene, as well as natural and synthetic fibers, and other combinations, are demonstrated in multiple ways.

[0326] This method offers the advantages of ease of addition and lower viscosity.

[0327] Examples of applications include reinforced hot melts; reactive hot melts; continuous or discontinuous hot melt coated articles, webs, and films; continuous or discontinuous hot melt coated fibers; and hot melt adhesive articles, including fibers, ropes, shapes, dots, and preform articles made from monomers, polymers, and / or oligomers.

[0328] One of the advantages is that it adheres to the substrate with minimal excess adhesive material.

[0329] Some uses of the present invention include: • Conductive materials • Thermally conductive materials • Recyclable materials • Architectural and industrial coatings • Sealant - Strength, durability, and sealant adhesion. Improved elasticity and flexibility. Resistance to UV irradiation and humidity, better adhesion. • Composite materials - fracture toughness, high modulus of elasticity, • Adhesives - fracture toughness, high modulus of elasticity, • Pressure-sensitive adhesive • Pressure-sensitive adhesive • Drug Delivery - These particles can also be designed to release drugs in a controlled manner, enabling 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 characteristics - • Coating polishing strength ·plywood • Geotextiles (road construction, railway construction, revetment construction) Roofing materials, insulating materials, covering materials, acoustic materials, and structural laminates

[0330] Examples of final or intermediate products Examples of final products or intermediate products include the following: • Additives in coatings to provide various properties such as scratch resistance, UV protection, and water repellency. • Automotive coatings to improve durability. • Fabric coatings that provide various properties such as water repellency, stain resistance, and antimicrobial activity. • A porous ceramic material having a specific pore size and distribution. The polymer template is removed during firing, leaving behind the porous ceramic material with its properties adjusted. • Shoes - lining, main body components, etc., and their final structures. Apparel - Linings, main body components, etc., and their final structures. • Packaging - lining, main components, etc., and their final structures, sealing, and fasteners. • Boxes - linings, body parts, etc., and their final structures. • Decorative items made of flexible laminated materials (tablecloths, drapes, etc.). ·furniture. • Oil and gas film products.

[0331] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to the extent of this disclosure. In case of any conflict, this specification, including its definitions, shall prevail.

[0332] Unless otherwise explicitly stated, trademarks shall be shown in capital letters.

[0333] Unless otherwise specified, all percentages, parts, ratios, etc., are based on weight.

[0334] Unless otherwise specified, pressure expressed in psi is gauge pressure, and pressure expressed in kPa is absolute pressure. However, pressure differences are expressed as absolute values ​​(for example, pressure 1 is 25 psi higher than pressure 2).

[0335] Where a quantity, concentration, or other value or parameter is given as a range, or as an enumeration of upper and lower limits, this is understood to specifically disclose all ranges formed from any pair of any upper and lower limits, regardless of whether the ranges are disclosed separately. Where a range of numbers is described herein, unless otherwise specified, the range is intended to include its endpoints, as well as all integers and fractions within that range. The scope of this disclosure is not intended to be limited to the specific values ​​described when defining the range.

[0336] Where the term “approximately” is used, it means that a particular effect or result can be obtained within a certain tolerance range, and a person skilled in the art would know how to obtain such tolerance. Where the term “approximately” is used to describe an endpoint of a value or range, this disclosure should be understood to include the specific value or endpoint referred to.

[0337] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof, are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to those elements alone and may include other elements that are not expressly enumerated or that are specific to such process, method, article, or apparatus.

[0338] The transitional phrase "consisting of" excludes any element, process, or component not specified in the claim, and excludes from the claim the inclusion of materials other than those described, except for impurities that are typically associated with them. If the phrase "consisting of" appears in a clause of the claim rather than immediately following the preamble, the phrase is limited to the elements described in that clause only, and other elements are not excluded from the claim as a whole.

[0339] The transitional phrase "consisting essentially of" limits the scope of the claim to a particular material or process and does not substantially affect the basic and novel features of the claimed invention. Claims "consisting essentially of" occupy an intermediate position between closed claims written in the form "consisting of" and fully open claims drafted in the form "including". Optional additives as defined herein are not excluded from the composition by the term "consisting essentially of".

[0340] Furthermore, unless explicitly stated otherwise, "or" and "and / or" are inclusive and not exclusive. For example, condition A or B, or A and / or B, is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0341] The use of “a” or “an” to describe various elements and components in this specification is solely for convenience and to give a general meaning to the disclosure. This description should be read as including one or at least one, and the singular form includes the plural form unless it is clear that it has a particular meaning other than that.

[0342] All references cited herein are incorporated by reference as if they were fully included herein.

[0343] Experimental example Example 1 - Methylene malonate polymerization via anionic polymerization composition This embodiment is a curable composition containing matrix particles, (a) Methylene malonate monomer and (b) Stabilizer solution and (c) an activator, (i) The activator contains cations at a level of 0.1 to 500 ppm, (ii) The present invention relates to a curable composition comprising an activator encapsulated in heat-deformable and / or heat-soluble matrix particles (e.g., carbon nanostructures) which also contain an RF susceptor.

[0344] compound The formulation is composed of the following by weight percentages, with other modifications made as desired: 1.20% to 70.0% of difunctional or greater methylene malonate monomers, oligomers, or resins. 2. Diethyl, dipropyl, dibenzyl, diisobornyl, or similar methylene malonate monomers, 20% to 70% 3. Acid stabilizer solution 0.1%~0.7%.

[0345] For the above formulation, the matrix particles, measuring 50 to 5000 nanometers, contain 90% paraffin wax, 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.

[0346] Matrix research Overall, the activator concentration ranges from 0.5 ppm to 500 ppm, which is achieved by varying the matrix particle concentration from 0.5% to 10%, as well as by the power level, which determines the appropriate frequency for the application itself, and therefore the time required for polymerization to activate the particles.

[0347] MF transparent filler The formulations produced above can then be adjusted by using chemically neutral, optionally dry RF transparent fillers, such as minerals like calcium carbonate, glass or glass powder, polymer powder, wood or other organic powder, silica, silicate, and ceramic. If moisture is a concern, a combination of transition metal accelerators, particularly copper hexanoate and iron, specifically ferrocene, can be used.

[0348] Curing, substrate, and container Varying the formulation will vary the curing rate, and therefore the heat generated during polymerization. Therefore, it is advisable to begin by placing a small amount of the formulation so that the thin film fits between two glass slides, thereby minimizing the material while still creating anaerobic conditions and allowing observation. In the next step, spacers can be added to create a thicker bond. In the next step, it can be transferred to a narrow test tube and / or syringe body. Then, it can be scaled up to a larger test tube and / or syringe body. Finally, it can be scaled up to a small beaker. To avoid hazardous situations, larger volume material assemblies and / or containers can be placed in oil and / or water to control the heat conduction of the exothermic reaction.

[0349] Essentially, to ensure that the required RF energy is properly transmitted, it is desirable that the container or part of the container be made of an RF-transparent material.

[0350] Example 2 - Free radical polymerization via anaerobic polymerization composition This embodiment is a curable composition, (a) Acrylate and / or methacrylate monomers, (b) A hydroperoxide or perester initiator, (c) an activator, (i) The activator contains a copper ion source at a copper level of 0.1 to 100 ppm, (ii) The present invention relates to a curable composition comprising an activator encapsulated in heat-deformable and / or heat-soluble matrix particles that also contain an RF susceptor.

[0351] compound The formulation is composed of the following by weight percentages, with other modifications made as desired: 1. Triethylene glycol dimethacrylate, urethane diacrylate, or epoxy diacrylate 20%~70.0% 2. Lauryl, ethyl, methyl, ethylhexyl, cyclohexyl, isobornyl methacrylate, 20%~70% 3. Cumene hydroperoxide 0.5%~3.0% 4. Stabilizer solution * 0.3%~0.7% 5. Saccharin 0.1%~0.5%

[0352] To these formulations, the following are added: matrix particles of 50 to 5000 nanometers containing 90% by weight of one or more of the following matrices: paraffin wax, olefin polymer, oligomeric wax, or similar; 8% carbon nanotubes; and 2% copper ethylhexanoate activator. These components are added so that the particles exhibit a copper content of 0.6 ppm in the final composition.

[0353] Alternatively, instead of 2% copper, 0.06% can be added to a 50% particle dispersion formulation containing 2% ferrocene in the particles.

[0354] Matrix Research: The concentration of copper hexanoate ranged from 0.6 ppm to 60 ppm, which was achieved by varying the concentration of matrix particles, the percentage of the compound in the matrix particles from 0.5% to 10%, and the power level, which determines the appropriate RF wavelength for the application itself, and therefore the time required to activate the particles and thus polymerize them.

[0355] RF transparent filler The formulations created above were prepared by using chemically neutral, optionally dry RF transparent fillers such as calcium carbonate and many other minerals, glass or glass powder, polymer powder, wood or other organic powder, silica, silicate, and ceramic. When moisture was a problem, a combination of transition metal accelerators, particularly copper hexanoate and iron, specifically ferrocene, was used.

[0356] Curing, substrate, and container Varying the formulation will vary the curing rate, and therefore the heat generated during polymerization. Therefore, first, a small amount of the formulation is placed so that the thin film fits between two glass slides, thereby minimizing the material while still creating anaerobic conditions and allowing observation. Next, a spacer is added to create a thicker bond. Then, it is transferred to a narrow test tube and / or syringe body. Next, it is scaled up to a larger test tube and / or syringe body. Next, it is scaled up to a small beaker. To avoid hazardous situations, larger volume material assemblies and / or containers are placed in oil and / or water to control the heat conduction of the heat. Essentially, an RF-transparent material is desirable for the container or part of the container so that the required RF energy can be properly transferred.

[0357] Example 3 - Process for using commercially available microparticles as a core This study demonstrates the use of microparticles as cores for matrix particles carrying activators to initiate curing in one-component adhesive formulations. The main objective of this study is to demonstrate the use of commercially available PMMA, already present on micro / nanoscale particles, as a carrier for acrylic activation by attaching a copper activator to the surface of a commercially available particle core.

[0358] [Table 2] **The MX-500ML, MP-1441, and MX-180TA were supplied by Soken Corporation, Japan, while the XX6666Z was supplied by Sekisui Kasei, Japan.

[0359] To evaluate the conditions for preparing matrix particles using various commercially available PMMA particles as the core of the matrix particles, the following formulations were prepared.

[0360] Formulation 1 - Commercial PMMA (MX-500ML) (2g) was first filtered and washed with a 10% (100mL) sodium hydroxide solution, then with a 10% (10mL) cupric chloride solution, rinsed with DI water, and dried.

[0361] Formulation 2 - Commercial PMMA (MX-500ML) (2g) was first filtered and washed with a 10% (100mL) sodium hydroxide solution, then with a 10% (10mL) cupric chloride solution, rinsed with DI water, and dried.

[0362] Formulation 3 - Commercial PMMA (MP-1441) (2g) was filtered and washed with a 10% (100mL) sodium hydroxide solution, followed by a 10% (10mL) cupric chloride solution, rinsed with DI water, and dried.

[0363] Formulation 4 - Commercial PMMA (XX-6666Z) (2g) was filtered and washed with a 10% (100mL) sodium hydroxide solution, followed by a 10% (10mL) cupric chloride solution, rinsed with DI water, and dried.

[0364] Formulation 5 - Commercial PMMA (MP-1441) (5g) was sonicated with copper(II) 2-ethylhexanoate (1g) in isopropanol, and then filtered and washed with additional isopropanol.

[0365] Formulation 6 - Commercial PMMA (MX-180TA) (2g) was ultrasonically treated with cupric chloride (0.125g) in isopropanol, and then filtered and washed with additional isopropanol.

[0366] Formulation 7 - Commercial PMMA (MX-180TA) (4g) was sonicated together with copper(II) 2-ethylhexanoate (0.21g) in isopropanol, and then filtered and washed with additional isopropanol.

[0367] Formulation 8 - Commercial PMMA (MX-180TA) (4g) was sonicated together with cupric chloride (0.2g) in isopropanol and then vacuum filtered.

[0368] Example 4 - Preparation of particle cores by emulsion polymerization The main objective of the study was to prepare nano- and microparticle cores through emulsion polymerization, particularly the emulsion polymerization of methacrylate. An exemplary reaction diagram is shown in Figure 18. To emulsion polymerization into nanoparticles, formulations were prepared using an oil-in-water emulsion—methacrylate in water.

[0369] Experiment 1: Methyl methacrylate (3 mL) was added to DI water (16 mL) at 70°C and emulsified under inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (10-15 mg) and stirred for 30 minutes.

[0370] Experiment 2: Methyl methacrylate (3 mL) was added to DI water (16 mL) at 70°C and emulsified under inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (10-15 mg) and the mixture was stirred at 450 rpm for 40 minutes.

[0371] Experiment 3: Methyl methacrylate (3 mL) was added dropwise to DI water (16 mL) at 70°C over 30-40 minutes and emulsified under inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (10-15 mg) and the mixture was stirred for 40 minutes.

[0372] Experiment 4: Copper(II) 2-ethylhexanoate was dissolved in methyl methacrylate (3 mL) and injected into DI water (16 mL) at 70°C under inert gas conditions. ((2,2-azobis)2-methyl-propionamidine) dihydrochloride (10-15 mg) was added and the mixture was stirred at 350 rpm for 40 minutes.

[0373] Example 5 - Process for preparing hollow particle cores This study demonstrates a method for preparing hollow particle-core structures. Representative SEM images of hollow particles are shown in Figure 7, and representative SEM images of hollow core particles combining SPION and copper are shown in Figure 8.

[0374] Experiment 1 A solution of 5-6% w / v PMMA (120,000 g / mol) dissolved in dichloromethane (DCM) was added dropwise to an aqueous medium of polyvinyl alcohol (0.5-0.6% w / v) and stirred at 500-550 rpm for 10-15 minutes. The solution was left to stand overnight or for 12-18 hours until the DCM evaporated. The hollow particles were filtered and washed three times with isopropanol and then dried again.

[0375] Experiment 2 A 5-6% w / v PMMA (15,000 g / mol) solution dissolved in dichloromethane was added dropwise to an aqueous medium of polyvinyl alcohol (0.5-0.6% w / v) and stirred at 500-550 rpm for 10-15 minutes. The solution was left to stand overnight or for 12-18 hours until the DCM evaporated. The hollow particles were filtered and washed three times with isopropanol and dried again.

[0376] Experiment 3 A first solution of copper(II) 2-ethylhexanoate (12.5 mg) dissolved in dichloromethane was prepared. A second solution of 5-6% w / v PMMA (15,000 g / mol) dissolved in the first solution was added dropwise to an aqueous medium of polyvinyl alcohol (0.5-0.6% w / v) and stirred at 500-550 rpm for 10-15 minutes. The final solution was left to stand overnight or for 12-18 hours until the DCM evaporated. The hollow particles were filtered and washed three times with isopropanol and dried again.

[0377] Experiment 4 A dispersion of SPION (12.5 mg) in dichloromethane was prepared. 5-6% w / v PMMA (15,000 g / mol) dissolved in the SPION / dichloromethane dispersion was added dropwise to an aqueous medium of polyvinyl alcohol (0.5-0.6% w / v) and stirred at 500-550 rpm for 10-15 minutes. The solution was left to stand overnight or for 12-18 hours until the DCM evaporated. The hollow particles were filtered and washed three times with isopropanol and then dried again.

[0378] Experiment 5 A dispersion of oleic acid-modified SPION (12.5 mg) in dichloromethane was prepared. 5-6% w / v PMMA (15,000 g / mol) dissolved in the SPION / dichloromethane dispersion was added dropwise to an aqueous medium of polyvinyl alcohol (0.5-0.6% w / v) and stirred at 500-550 rpm for 10-15 minutes. The solution was left to stand overnight or for 12-18 hours until the DCM evaporated. The hollow particles were filtered and washed three times with isopropanol and then dried again.

[0379] Experiment 6 Dispersions of oleic acid-modified SPION (12.5 mg) and copper(II) 2-ethylhexanoate (12.5 mg) in dichloromethane were prepared. 5-6% w / v PMMA (15,000 g / mol) dissolved in the SPION / dichloromethane dispersion was added dropwise to an aqueous medium of polyvinyl alcohol (0.5-0.6% w / v) and stirred at 500-550 rpm for 10-15 minutes. The solution was left to stand overnight or for 12-18 hours until the DCM evaporated. The hollow particles were filtered and washed three times with isopropanol and then dried again.

[0380] Example 6 - Process for preparing a core by fusing a susceptor and a catalyst This study demonstrates the remote microwave activation of susceptors within matrix particles. The matrix used in these studies was prepared as a fusion by combining the susceptors and other components of matrix particles. The matrix particles were exposed to microwaves to release activators and exhibit their functions. For example, in some cases, microwaves were used to heat the susceptors and carbon nanostructures, releasing copper catalysts from the matrix particles and catalyzing polymerization reactions.

[0381] Experiment 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 with a heat gun. Solutions A and B were combined very slowly while continuously heating. 0.5% copper(II) 2-ethylhexanoate was added to solutions A and B. The solution was heated at 110°C with continuous stirring until most of the xylene evaporated. Before all of it evaporated, 10% carbon nanostructures were added and mixed with high shear. Once enough xylene had evaporated and the solution had become a paste, the solution was added to ethanol and precipitated. The solid was crushed with water in a blender and dried overnight to obtain a powder. The powder was sieved through a micron mesh to obtain core particles.

[0382] Experiment 2 A dispersion of 0.1 g of carbon nanostructure pellets in 30 mL of dichloromethane was prepared. While mixing at 700 rpm, a solution of 3 g of hexadecyltrimethylammonium bromide (CTAB) dissolved in 10 mL of isopropanol and 20 mL of dichloromethane was added. Copper(II) 2-ethylhexanoate was added to the solution along with 10 g of solid plasticizer (Benzoflex® 352) while continuously stirring. The sample was left to stand while stirring until dry.

[0383] Experiment 3 A mixture of 0.1 g of carbon nanotubes containing 0.2 g of CTAB in 30 mL of dichloromethane was prepared and sonicated at 30% power for 15 minutes. Further 50 mL of dichloromethane was added, and the sample was sonicated again at 30% power for another 15 minutes. 9.9 g of Benzoflex™ 352 (solid plasticizer) and 1 g of copper(II) 2-ethylhexanoate were added and mixed by hand. A stirring rod was added to the sample, and the mixture was left to stand on a hot plate at 35°C and 700 rpm while stirring, maintaining the suspension of particles while evaporating the dichloromethane.

[0384] Experiment 4 A mixture of 0.11 g of experimental particles was dispersed in 10 mL of dimethyl malonate by sonication for 10 minutes. A drop of these particles was placed on a glass microscope slide and microwaved for 60 seconds at 800 W / 4 V to test it.

[0385] Example 7 - Process for coating microparticles with a susceptor This study demonstrates a method for using susceptors such as carbon nanotubes (CNTs) or carbon nanomaterials (CNS) to coat microparticles, such as commercially available PMMA microparticles.

[0386] Experiment 1 In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water. The mixture was then sonicated at 20% amplitude for 30 minutes using a microprobe sonicator. In a separate flask, 300 mg of CNTs were added to 120 ml of water. The mixture was sonicated at 10% amplitude for 15 minutes using a probe sonicator. The PMMA-water dispersion was placed in a beaker and continuously stirred at room temperature to prevent sedimentation of the PMMA particles. Next, 10 ml of the CNTs dispersed in water was placed in a syringe and added to the PMMA dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0387] Experiment 2 In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water. The mixture was then sonicated at 20% amplitude for 30 minutes using a microprobe sonicator. In a separate flask, 300 mg of CNS was added to 120 ml of water. This mixture was sonicated at 10% amplitude for 15 minutes in the sonicator. The PMMA-water dispersion was placed in a beaker and continuously stirred at room temperature to prevent sedimentation of the PMMA particles. Next, 10 ml of the CNT dispersion in water was placed in a syringe and added to the PMMA dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were separated using a centrifuge.

[0388] Experiment 3 In this experiment, 1 ml of PMMA, prepared using the emulsion polymerization method previously described, was added to 9 ml of water. In a separate flask, 300 mg of CNTs were added to 120 ml of water. The mixture was sonicated for 15 minutes at 10% amplitude using a microprobe sonicator. 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 taken into a syringe and added dropwise to the CNT dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0389] Example 8 - Process for preparing microparticles via emulsion copolymerization This study provides a method for functionalizing PMMA by copolymerizing it with various copolymers, including poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) dimethacrylate (PEGDMA), stearyl methacrylate, and methacrylic acid.

[0390] Experiment 1 Methyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (20 mg) and stirred for 30-40 minutes. An additional 20 mg of AIBN was added together with 1.2 mL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 minutes.

[0391] [ka]

[0392] Experiment 2 Methyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (20 mg) and stirred for 10 minutes. An additional 20 mg of AIBN was added together with 1.2 mL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 minutes.

[0393] Experiment 3 Methyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (20 mg) and stirred for 10 minutes. An additional 20 mg of AIBN was added together with 120 μL of poly(ethylene glycol) methacrylate (PEGMA) and stirred for 40 minutes.

[0394] Experiment 4 Methyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (20 mg) and stirred for 10 minutes. An additional 20 mg of AIBN was added to 120 μL of poly(ethylene glycol). It was added together with dimethacrylate (PEGDMA) and stirred for 40 minutes.

[0395] [ka]

[0396] Experiment 5 Methyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (20 mg) and stirred for 10 minutes. An additional 20 mg of AIBN was added together with 1.2 mL of poly(ethylene glycol) dimethacrylate (PEGDMA) and stirred for 40 minutes.

[0397] Experiment 6 A solution of sodium dodecyl sulfate (SDS) (0.5 g) dissolved in hydroxyethyl methacrylate (HEMA) (15 g) was prepared. This solution was transferred to DI water (185 g) in a round-bottom flask in a 70°C bath and stirred at high speed. Heating was stopped, and the solution was continued to be stirred while adding AIBN (0.2 g).

[0398] Experiment 7 The 64 mL of DI water in the flask was degassed and heated to 70°C with stirring at 670 rpm for 20 minutes. In the next step, 1 g of stearyl methacrylate was dissolved in 9 mL of methyl methacrylate. This solution was added dropwise to water over 15 minutes with constant stirring in the presence of an inert gas. After the addition, ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (40 mg) was added to the emulsion, and the mixture / solution was stirred for a further 1 hour.

[0399] [ka]

[0400] Experiment 8 A flask containing 64 mL of DI water was degassed, and its contents were heated to 70°C while stirring at 670 rpm for 20 minutes. Then, separately, 5 g of stearyl methacrylate was dissolved in 5 mL of methyl methacrylate. This solution was added dropwise to the flask over 15 minutes while stirring at a constant temperature in the presence of an inert gas. After the addition, ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (40 mg) was added to the emulsion, and the mixture was stirred for a further 1 hour.

[0401] Experiment 9 The 64 mL of DI water in the flask was degassed, and the contents were heated to 70°C while stirring at 670 rpm for 20 minutes. Next, 5 mL of methacrylic acid was dissolved in 5 mL of methyl methacrylate. Under constant stirring under an inert gas, this solution was added dropwise to water over 15 minutes. After the addition, ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (40 mg) was added to the emulsion, and the mixture was stirred for a further 1 hour.

[0402] [ka]

[0403] Experiment 10 The 64 mL of DI water in the flask was degassed, and the contents were heated to 70°C while stirring at 670 rpm for 20 minutes. Next, 1 mL of methacrylic acid was mixed with 5 mL of methyl methacrylate. Under constant stirring under an inert gas, this solution was added dropwise to water over 15 minutes. After the addition, ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (40 mg) was added to the emulsion, and the mixture was stirred for a further 1 hour.

[0404] Experiment 11 Methyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((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 for 40 minutes under an inert gas.

[0405] Experiment 12 Glycidyl methacrylate (12 mL) was added dropwise to DI water (64 mL) at 70°C and emulsified in the presence of an inert gas. The polymerization reaction was catalyzed with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (AIBN) (20 mg), and the mixture was stirred for 40 minutes.

[0406] Example 9 - Process for coating commercially available microparticles with a commercially available emulsion. The objective of this study was to coat commercially available PMMA particles as a core having a shell containing a susceptor and / or activator through a simple coating process.

[0407] Experiment 1 In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water in a beaker. The mixture was then sonicated in an ultrasonic device at 20% amplitude for 30 minutes. Simultaneously, commercially available SP-05032022-3: CNT dispersed in polyurethane was diluted 100-fold and added to a separate beaker. The PMMA-water dispersion was continuously stirred at room temperature to prevent sedimentation of the PMMA particles. Next, 10 ml of polyurethane-dispersed CNT was added to the PMMA dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0408] Experiment 2 In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water in a beaker. The mixture was then sonicated in an ultrasonic device at 20% amplitude for 30 minutes. Simultaneously, commercially available SP-05032022-05: Epoxy-CNT was diluted 100-fold and added to a separate beaker. The PMMA-water dispersion was continuously stirred at room temperature to prevent sedimentation of the PMMA particles. Next, 10 ml of diluted Epoxy-CNT was added to the PMMA dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0409] Experiment 3 In this experiment, 250 mg of PMMA (Soken MX-500ML) was added to 50 ml of water in a beaker. The mixture was then sonicated in an ultrasonic device at 20% amplitude for 30 minutes. Simultaneously, commercially available SP-05032022-3: CNT dispersed in polyurethane was diluted 10-fold and added to a separate beaker. The PMMA-water dispersion was continuously stirred at room temperature to prevent sedimentation of the PMMA particles. Next, 10 ml of polyurethane-dispersed CNT was added to the PMMA dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0410] Example 10 - Process for using carbon nanostructures as susceptors This study demonstrates the use of commercially available carbon nanostructures as radiofrequency (RF) radiation susceptors within matrix particles to assist in catalyst release, thereby initiating polymerization reactions. For example, heating the susceptor causes melting of the particle matrix, which releases chemical components such as copper salt catalysts and initiates polymerization. The objective of this study was to use commercially available PMMA particles as carriers for copper activators.

[0411] The particles generated in this study's experiments were prepared by using commercially available particles with micro to nanoscale diameters as carriers for the acrylic activator, and attaching the activator to the surface of the core of the matrix particles.

[0412] The microparticles from Example 6 described above were used in the following heating time measurements.

[0413] Experiment 1 Microparticles from Example 6 were taken and added to an acrylic monomer formulation consisting of 3 parts triacrylated monomer (OTA480), 1 part polyfunctional acrylic monomer (EBECRYL® 896), 1 part polyurethane acrylate (EBECRYL® 8811) (all from Allnex Co), and 5000 ppm 4-methoxyphenol (MEHQ), 2% cumyl hydroperoxide (CHP), and 2% 4,N,N-trimethylaniline (DMPT), with 0.10 g of acrylic monomer per 3 g of monomer. The data from the heating experiment are shown in Table 4 below.

[0414] [Table 3]

[0415] Example 11 - Evaluation of the stability of particle cores prepared using CNS susceptors Research conducted using foam The foam curing test was performed by cutting two pieces of foam into 4-inch x 4-inch cubes. The sample from Experiment 6 of Example 9 tested above was pipetted onto one piece of foam so that it uniformly covered one side of the cube and the layer was thick enough to protrude over the pores of the foam. The second cube was placed on top of the first cube, completely covering the sample. The foam cube was placed between two slides with spacers, and uniform pressure was maintained by clamping the glass slides with a rubber band. The clamped sample was placed in a microwave chamber under a thermal camera. To isolate the sample from direct heating, the sample was placed on an insulator inside the microwave chamber. The sample was microwaved at 800W for a preset time. After removing the sample from the microwave, the apparatus was carefully disassembled. To test whether the foam pieces were bonded together, the corners of the foam were gently pulled apart.

[0416] Type of foam tested: We used 1 / 2-inch Airtex high-density foam to create camper cushions, boat seats, chair pads, garden benches, and small foam cushions.

[0417] 1 / 8-inch divinyl mats and 1 / 2-inch vinyl foams are frequently used as structural core materials in composite laminates, delivering additional strength, rigidity, and insulation without adding weight. Generally, foams conform easily to shape and can be bonded to layers to add thickness.

[0418] Nomex honeycomb, made from aramid fibers, exhibits excellent flame-retardant properties.

[0419] Research conducted using composite materials The curing of bulk composites was evaluated using bare silicone molds. Each bare mold was filled with a 5cc volume at a time and placed in the center of the microwave under a thermal camera. Only one sample was placed at a time to ensure the sample remained within the thermal camera's field of view. The bare mold was microwaved at 800W for a predetermined time, removed from the microwave, and tested for changes in viscosity or curing.

[0420] Tested samples 1. Sample A: Acrylic adhesive formulation without activators (For details of the formulation, please refer to Experiment 1 in Example 9 above.) 2. Sample B: Acrylic adhesive compound + copper activator 3. Sample C: Acrylic adhesive compound + matrix particles (containing both susceptor and copper activator)

[0421] Results from experiments conducted at room temperature using Airtex foam: 1. Sample A: Did not harden after one month; this sample does not contain an activator. 2. Sample B: Cured within 30 minutes 3. Sample C: It cured within 30 seconds in a microwave, but did not cure at room temperature even after one month.

[0422] Results from experiments conducted at room temperature using divinyl mats, vinyl foam, and honeycomb: 1. Sample A: It did not harden even after one month, and this sample does not contain any activating agent. 2. Sample B: Cured within 30 minutes 3. Sample C: It cured within 30 seconds in a microwave, but did not cure at room temperature even after one month.

[0423] Results from experiments conducted using composite materials: 1. Sample A: It did not harden even after one month, and this sample does not contain any activating agent. 2. Sample B: Cured within 30 minutes. 3. Sample C: It hardened within 20 seconds in a microwave, but did not harden at room temperature even after one month.

[0424] This experimentally demonstrates the storage life of the matrix particles of the present invention while providing curing on demand.

[0425] Example B1: Nanotube-coated PMMA particles Matrix particles are prepared using one or more types of nanotubes, in accordance with U.S. Patent Application No. 18 / 055,302 by Malofsky et al., which is incorporated by reference as if fully described herein. The description is also provided in a set of prior 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 may or may not contain catalysts, co-catalysts, or accelerators, depending on the purpose for which the matrix particles are used.

[0426] The original PMMA particles can be prepared using emulsion polymerization, suspension polymerization, dispersion polymerization, and 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).

[0427] Furthermore, these can be purchased from companies such as Sekisui or Soken in Japan, for example. These particles can be prepared or obtained using various functional groups such as -OH, -NH, -COOH, and epoxy.

[0428] Nanotubes can be obtained from dozens of manufacturers, including cheaptubes.com, LG Chem (CNT division), and Tuball, Kumho Petrochemicals.

[0429] Here, we will use the following PMMA particles:

[0430] [Table 4] ** The MX-500ML, MP-1441, and MX-180TA were supplied by Soken Corporation, Japan, while the XX6666Z was supplied by Sekisui Kasei, Japan.

[0431] I. Process for producing PMMA particles Experiment B1. Add 1-methyl methacrylate (3 mL) to DI water (16 mL) at 70°C and emulsify under inert gas. Catalytic polymerization with ((2,2-azobis)2-methyl-propionamidine)dihydrochloride (10-15 mg) and stir for 30 minutes.

[0432] Experiment B1.2: This study provides a method for functionalizing PMMA by copolymerizing it with various copolymers, including poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) dimethacrylate (PEGDMA), stearyl methacrylate, and methacrylic acid.

[0433] II. Process for coating with nanotubes This study demonstrates a method for using susceptors such as carbon nanotubes (CNTs) or carbon nanomaterials (CNS) to coat microparticles, such as commercially available PMMA microparticles.

[0434] Experiment B1.3: In this experiment, 250 mg of PMMA (Soken MX-500ML) is added to 50 ml of water. Then, it is sonicated for 30 minutes at 20% amplitude using a microprobe sonicator. In a separate flask, 300 mg of CNTs is added to 120 ml of water. It is sonicated for 15 minutes at 10% amplitude using a probe sonicator with SDS surfactant. The dispersion of PMMA and water is placed in a beaker and continuously stirred at room temperature to prevent sedimentation of PMMA particles. In the next step, 10 ml of CNT dispersed in water is taken into a syringe and added dropwise to the PMMA dispersion at 0.5 ml / min using a syringe pump. The sample is left overnight to allow the coated PMMA particles to settle. Then, the particles are separated using a centrifuge.

[0435] The particles containing 3.2% by weight of CNS, prepared in Experiment B1.3, were dispersed in an acrylic monomer formulation at concentrations of 25% by weight and 75% by weight using a Flacktek speed mixer set to 2,000 RPM for 1 minute and 30 seconds. The acrylic formulation contained 3 parts triacrylated monomer (OTA480), 1 part polyfunctional acrylic monomer (EBECRYL® 896), 1 part polyurethane acrylate (EBECRYL® 8811) (all from Allnex Co), and 5,000 ppm of 4-methoxyphenol (MEHQ), 2% cumyl hydroperoxide (CHP), and 2% 4,N,N-trimethylaniline (DMPT).

[0436] Acrylic formulations containing particles were degassed using a vacuum chamber for 30 minutes. Then, a 100% PMMA sample containing 3.2% CNS, as well as acrylic formulations containing 0%, 25%, and 75% particles, were applied to 1 / 8-inch polycarbonate plaques at 4 mil and pressed in a hot press set to 230°F for 30 minutes. The electrical resistivity of the cured films was measured using a surface resistivity meter and is shown in the table below:

[0437] [Table 5]

[0438] The electrical resistivity versus CNS filling amount shown in plot L2 is 1.0 × 10 for CNT filling amounts of 0 to 3.2%. 13 ~6.0×10 3 This shows a steady decrease in electrical resistivity to ohms. This clearly demonstrates the effectiveness of microparticles for delivering CNTs to acrylic formulations.

[0439] 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 a separate flask, 300 mg of CNTs were added to 120 ml of water. The mixture was sonicated for 15 minutes at 10% amplitude using a microprobe sonicator. 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 taken into a syringe and added dropwise to the CNT dispersion at a rate of 0.5 ml / min using a syringe pump. The sample was left overnight to allow the coated PMMA particles to settle. The particles were then separated using a centrifuge.

[0440] Example B2: Nanotube-containing PMMA particles prepared by fusion 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 with a heat gun. Solutions A and B were combined very slowly while continuously heating. 0.5% copper(II) 2-ethylhexanoate was added to solutions A and B. The solution was heated at 110°C, with continuous stirring until most of the xylene evaporated. Before all of it evaporated, 10% carbon nanostructures were added and mixed with high shear. Once enough xylene had evaporated and the solution had become a paste, the solution was added to ethanol to precipitate. The solid was crushed with water in a blender and dried overnight to obtain a powder. The powder was sieved through a micron mesh to obtain core particles.

[0441] Example B3: Coating using a functional nanoparticle emulsion of nanotube-coated particles After coating the particles from Example B1 with nanotubes to the desired extent, they are washed and dried, or left in a solvent for a subsequent coating reaction or process using a selected material that opposes van der Waals forces. (The applicants do not wish to be bound by any theory considered in this disclosure.) In this nanowax, epoxy and PUD (polyurethane dispersion) are nanoparticle emulsion and dispersion, respectively. The PUD is purchased from Covestro, and the epoxy emulsion is purchased from Westlake.

[0442] Functional nanoparticle emulsions and dispersions can be obtained from manufacturers including Michelman, Covestro, BYK, and Westlake.

[0443] Here, we use the following functional nanoparticle emulsions and / or dispersions: A.ME98040M1(Michelaman) B.EPI-REZ3514-W-56(Westlake) C.Baybond PU405 (Covestro) D.Aqacer581, 532, 1061(BYK)

[0444] Experiment B3.1: The functional nanoparticle emulsion and dispersion in water are added dropwise to 250 mg of particles from Example B1 using a syringe pump. The sample is left overnight to allow the coated particles to settle. The particles are then separated using a centrifuge.

[0445] Example B4: Coating using a monofunctional reactive material with nanotube-coated particles After coating the particles of Example 1 with nanotubes to the desired extent, they are washed and dried, or left in a solvent for a subsequent coating reaction or process using a selected material that opposes van der Waals attraction, in which case a monofunctional reactive material is used. These studies can be carried out by varying the length of the aliphatic chains.

[0446] These are common materials readily available from manufacturers such as BASF and Evonik, and similarly from Sigma Aldrich for laboratory use.

[0447] Examples of materials include: A. Stearic acid B. Octanoic acid C. Oleic acid D. Stearyl alcohol E. Aliphatic amines F. Chitosan G. Diocatylamine, Hexadecylamine

[0448] Experiment B4.1: Suspend particles from Experiment B1.3 containing alcohol functional groups in anhydrous MEK (methyl ethyl ketone) or isopropyl acetate, dimethyl carbonate, cyclohexanone, or 2-methyltetrahydrofuran. Select a solvent in which the particles do not dissolve. React these with oleic acid, stearic acid, and octanoic acid, or other branched or linear fatty acids under standard Steglich-type ester conditions.

[0449] Test B4.2: Particles from Experiment B1.3 containing acidic functional groups were suspended in the anhydrous solvent described in Experiment 4.1 and reacted with fatty acid alcohols, not limited to stearyl alcohols, under standard Steglich-type ester conditions.

[0450] Experiment B4.3: Particles from Experiment B1.3 containing epoxy functional groups are suspended in the anhydrous solvent described in Experiment B4.1 and reacted with aliphatic primary and secondary amines, not limited to dioctylamine and hexadecylamine.

[0451] Example B5: Coating using a bifunctional material of nanotube-coated particles After coating the particles of Example B1 with nanotubes to the desired extent, they are washed and dried, or left in a solvent for a subsequent coating reaction or process using a selected material that opposes van der Waals attraction, in this case using a monofunctional reactive material. These studies can be carried out by varying the length of discontinuous aliphatic chains containing a bifunctional material. One is reactive, and the other is a protective (non-interfering) functional group. The reactive functional group is designed to react with the particles from Example B1, while the protected functional group is left on the outside for further manipulation for crosslinking.

[0452] These are common materials readily available from manufacturers such as BASF and Evonik, and similarly from Sigma Aldrich for laboratory use.

[0453] Examples of materials include: A. Adipic acid B. Adipic acid half-ester C. Propylenediamine D. Ethylenediamine E.BOC Monoprotective Propylenediamine

[0454] Experiment B5.1: Particles from Experiment B1.3 containing alcohol functional groups were suspended in anhydrous MEK (methyl ethyl ketone) or isopropyl acetate, dimethyl carbonate, cyclohexanone, or 2-methyltetrahydrofuran. A solvent in which the particles do not dissolve was selected. These were then reacted with a difunctional carboxylic acid such as adipic acid or adipic acid hemiester.

[0455] Experiment 5.2: Particles from Experiment B1.3 containing acidic functional groups were suspended in the anhydrous solvent described in Experiment B4.1 and reacted with propylenediamine using carbodiimide / n-hydroxybenzotriazole (HOBt) coupling.

[0456] Example B6: Viscosity effect - Blend of materials containing carbon nanotubes, carbon nanotube-coated particles, or carbon nanotube-containing particles, and coated carbon nanotube-coated particles or coated carbon nanotube-containing particles.

[0457] Here, we demonstrate that carbon nanotubes and / or carbon nanotube-coated particles have very high viscosity due to the associated van der Waals effect, but coated particles, especially those with repulsive coatings, do not.

[0458] Procedure: Particles from Examples B1, B2, B3, B4, and B5 are mixed into polymerizable compositions for coatings and adhesives using a higher shear, sonication, and high-speed mixing process. The viscosity of the resulting material is measured using a Ford Cup viscometer or Brooke viscometer.

[0459] Example B7 Performance Effect - I In one embodiment, the present invention relates to blending a polymerizable composition with carbon nanotube-coated particles and / or carbon nanotube-containing particles, polymerizing the matrix, and evaluating the physical effects on strength, impact resistance, modulus of elasticity, toughness, etc.

[0460] Here, we demonstrate that carbon nanotube-coated particles and / or carbon nanotube-containing particles now have lower viscosity for lower cost, simpler and easier processing and filling, and subsequently also provide slightly lower, the same, or improved physical performance in the final polymerized composition.

[0461] Procedure: Cure the polymerizable composition described in Example B6 under standard conditions. Test the performance of the resulting coating for hardness, for example, through an indentation test and a rubber polishing test. Perform a cross-hatch adhesion test and visual comparison with a standard.

[0462] Polymerizable compositions containing particles are cast and cured into thin films, and their tensile, flexural strength, and modulus are tested. Dynamic mechanical analysis (DMA) is used to measure the viscoelastic response of the sample under vibrating loads, monitored against temperature, time, or frequency.

[0463] Example B8 Performance Effect -- II In one embodiment, the present invention relates to blending polymerizable compositions comprising (i) carbon nanotube-coated particles, (ii) chemically functionalized carbon nanotube-coated particles, (iii) carbon nanotube-containing particles, and / or (iv) chemically functionalized carbon nanotube-containing particles. In the next step, such polymerizable compositions are polymerized and their physical effects on strength, impact resistance, modulus of elasticity, toughness, etc., are measured.

[0464] Here, we demonstrate that the aforementioned particles provide a material with lower viscosity for lower cost, simpler and easier processing and filling, and then also provide slightly lower, the same, or improved physical performance in polymerizable or partially reactive polymer compositions in which the particles are at least partially chemically bonded to the aforementioned polymer matrix.

[0465] The polymerized matrix is ​​tested by DMA under ASTM D4065, D4440, and D5279. The modulus of elasticity (or storage modulus, G'), viscosity (or loss modulus, G"), and damping coefficient (Tan D) are measured, correlated with temperature, frequency, or time.

[0466] Polymerization matrix, ASTMD638 / D-882 - Tensile Properties ASTMD790 - Bending properties of plastics ASTMD256 - Izod Impact Resistant Plastic ASTMD4812 - Testing the impact resistance of a plastic cantilever beam without notches under impact conditions.

[0467] Example Set C C1. Synthesis of CNT-modified PMMA brush microparticles via a bottom-up approach This study demonstrates a method for preparing CNT-modified "brush" microparticles, starting from MMA monomers and constructing micron-sized cores from monomers through a bottom-up approach. Surface-mounted CNTs provide a convenient method for delivering CNTs to polymer resin matrices for reinforcement.

[0468] Prepare 60 mL of SDS solution (0.1 mg / mL) in deionized (DI) water, then add methanol (30 mL). Add polyvinylpyrrolidone (PVP) (2.5 g) to the mixture and stir until dissolved. Next, introduce azoisobutyronitrile (AIBN) (0.2 g) into the solution and dissolve. In a separate container, homogenize a dispersion of CNT (4 mL) and surfactant (D-1038) (4 drops) in methanol (5 mL) by sonication for 10 minutes.

[0469] The sonicated CNT solution is slowly added to the reaction mixture containing PVP, methanol, and AIBN while continuously stirring. After stirring for 10 minutes, methyl methacrylate (MMA) (20 g) is slowly added to the reaction batch while maintaining a constant temperature of 70°C. The reaction is allowed to proceed at 70°C for 3 hours to ensure complete polymerization and particle formation in the CNT dispersion. Once the reaction is complete, the formed microparticles are filtered off from the reaction mixture.

[0470] C2. Modification of commercially available microparticles for producing brush particles with shells. This study demonstrates a method for preparing CNT-modified "brush" microparticles from commercially available PMMA particles. The CNTs on the surface of the microparticles provide a convenient method for delivering CNTs into the polymer resin matrix for reinforcement.

[0471] Commercial PMMA particles (50-60 g) with a diameter in the range of 1-5 micrometers were dispersed in a 10% solution of epoxy 1007F resin in 60 mL of tetrahydrofuran (THF). The PMMA particles were stirred until a homogeneous dispersion was achieved. A CNT dispersion in ethanol was added, and stirring was continued at 50°C for a further 1 hour. While continuing the procedure, the PMMA particle dispersion in epoxy resin was slowly injected into a 1% solution of polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP).

[0472] C3. Modification of commercially available microparticles for producing brush particles with low melting points. Commercially available PMMA particles with a diameter in the range of 1 to 5 micrometers were dispersed in epoxy 1004F resin and a THF solution (10% concentration). The PMMA particles were dispersed in the resin solution and stirred until homogeneous. A CNT dispersion in ethanol was added and stirred for a further 1 hour at 50°C. While continuing the procedure, the PMMA particle dispersion in epoxy resin was slowly injected into a 1% solution of polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP).

[0473] C4. Modification of commercially available microparticles for producing brush particles with low melting points Commercially available PMMA particles with a diameter in the range of 1 to 5 micrometers are dispersed in epoxy 1004F resin and solution (10% concentration). The PMMA particles are dispersed in the resin solution and stirred until homogeneous. The CNT dispersion in ethanol is added and stirred for a further 1 hour at 50°C. While continuing the procedure, the PMMA particle dispersion in epoxy resin is slowly injected into a 1% solution of polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP).

[0474] C5. Buried microparticles This study demonstrates a method for preparing embedded particle-core structures starting from commercially available microparticles. The embedded particles are used as the core of matrix particles. The embedding process involves treating the microparticles with a solvent such as IPA (isopropanol). Osmotic pressure on the microparticle surface and evaporation of the solvent create pores in the microparticles. Hydrophobic interactions result in the movement of catalysts and / or CNTs / CNS into the cavities. The embedded microparticles are converted into core-shell microparticles. The resulting core-shell microparticles offer the advantage of delivering CNTs to polymer resins.

[0475] C6. Embedded core-shell microparticles with PMMA shells Prepare a solution of polyvinyl alcohol (PVOH) (2g) in DI water (400g). Separately, prepare a dispersion of CNTs (0.8g) in isopropanol (100g). Add 10g of commercially available microparticles (1-10 microns) to the PVOH solution and disperse. Add the CNT dispersion to the PVOH solution. Stir the dispersion for 12-18 hours until the IPA (isopropyl alcohol) evaporates. During these 12-18 hours, voids are created on the surface of the microparticles due to the osmotic pressure of the IPA. As the solvent evaporates, the CNTs migrate into the voids due to hydrophobic interactions. Add the dried, buried microparticles containing the CNTs to clean water. Add stearyl methacrylate (5g) dropwise and carry out emulsion polymerization in the presence of an inert gas. The emulsion polymerization reaction is catalyzed with azoisobutyronitrile (AIBN) (20 mg), and the mixture is stirred for 40 minutes to form a PMMA shell.

[0476] Embedded core-shell microparticles with C7.PGMA shell Prepare a solution of polyvinyl alcohol (PVOH) (2g) in DI water (400g). Separately, prepare a dispersion of CNT (0.8g) in isopropanol (100g). Add 10g of commercially available microparticles (1-10g) to a PVOH solution and disperse. Add the CNT dispersion to the PVOH solution. Stir the dispersion for 12-18 hours until the IPA (isopropyl alcohol) evaporates. During these 12-18 hours, the osmotic pressure of the IPA creates cavities on the surface of the microparticles. As the solvent evaporates, the CNTs move into the cavities due to hydrophobic interactions. Add the dried, buried microparticles containing the CNTs to clean water. Add glycidyl methacrylate (GMA) (5g) dropwise and carry out emulsion polymerization in the presence of an inert gas. Catalyze the emulsion polymerization reaction with azoisobutyronitrile (AIBN) (20mg) and stir for 40 minutes to form a PGMA shell.

[0477] C8. Embedded microparticles with a PSMA shell created through emulsion polymerization. Prepare a solution of polyvinyl alcohol (PVOH) (2g) in DI water (400g). Separately, prepare a dispersion of CNTs (0.8g) in isopropanol (100g). Add 10g of commercially available microparticles (1-10 microns) to the PVOH solution and disperse. Add the CNT dispersion to the PVOH solution. Stir the dispersion for 12-18 hours until the IPA evaporates. During these 12-18 hours, voids are created on the surface of the microparticles due to the osmotic pressure of the IPA. As the solvent evaporates, the CNTs move into the voids due to hydrophobic interactions. Add the dried, buried microparticles containing the CNTs to clean water. Add stearyl methacrylate (SMA) (5g) dropwise and carry out emulsion polymerization in the presence of an inert gas. The emulsion polymerization reaction is catalyzed with azoisobutyronitrile (AIBN) (20 mg), and the mixture is stirred for 40 minutes to form a PSMA shell.

[0478] Embedded core-shell microparticles with C9.PU shell Prepare a solution of polyvinyl alcohol (PVOH) (2g) in DI water (400g). Separately, prepare a solution of copper 2-ethylhexanoate (0.8g) in isopropanol (100g). Add 10g of commercially available microparticles to the PVOH solution and disperse. Add the copper solution to the PVOH solution. Stir the dispersion for 12-18 hours until the IPA evaporates. During these 12-18 hours, voids are created on the surface of the microparticles due to the osmotic pressure of the IPA. As the solvent evaporates, the copper 2-ethylhexanoate moves into the voids due to hydrophobic interactions. Mix commercially available polyurethane-CNTs (10mL) in acetone into the dispersion as a coating for the embedded particles.

Claims

1. A plurality of matrix particles, including matrix particle A and / or matrix particle B, The matrix particle A comprises a core and, optionally, at least one shell. The aforementioned core, (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, (iii) at least one releaseable component, wherein the at least one releaseable component is embedded in the matrix material and capable of physically or chemically influencing a bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, The aforementioned at least one shell, (iv) Optionally, the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell, (v) at least one releaseable component, wherein the at least one releaseable component is embedded in the at least one shell and is capable of physically or chemically influencing the bulk physically or chemically modifiable 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 (vi) A matrix material wherein the matrix material is capable of completely or partially altering its physical and / or chemical properties, (vii) at least one releaseable component, wherein the at least one releaseable component is embedded in the matrix material and capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, The aforementioned at least one shell, (viiii) Optionally, the at least one susceptor component, wherein the at least one susceptor component is embedded in the at least one shell, (ix) the at least one releaseable component, wherein the at least one releaseable component is embedded in the at least one shell, and the at least one releaseable component is capable of physically or chemically influencing the bulk physically or chemically modifiable composition in contact with the plurality of matrix particles, A plurality of matrix particles, wherein at least one susceptor component and / or the emittable component can be activated through radio frequency (RF), microwave (MW) radiation, thermal activation, mechanical polishing, or a combination thereof.

2. The plurality of matrix particles according to claim 1, wherein the matrix material is derived from and / or comprises an organic material, a monomer material, an oligomer material, a polymer material, or a combination thereof.

3. A plurality of matrix particles according to claim 1 or 2, wherein the at least one susceptor and / or the at least one releaseable component is selected from the group consisting of fullerene compounds, 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 ferrous metals, one or more oxides of ferrous metals, SPION, one or more nonferrous metals, one or more oxides of nonferrous 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 claims 1 to 3, wherein the dimensions of the at least one susceptor and / or the at least one releaseable component are in the range of about 0.1 nm to about 1000 μm, and optionally, the at least one susceptor and / or the at least one releaseable component is functionalized and / or unfunctionalized.

5. A plurality of matrix particles according to any one of claims 1 to 4, wherein the at least one susceptor and / or the at least one releaseable component is located within the at least one shell, and the at least one susceptor and the at least one releaseable component are in direct or indirect contact.

6. The plurality of matrix particles according to any one of claims 1 to 5, wherein the matrix particles are partially or entirely coated on one or more layers of a deformable material, and optionally one or more of the layers contain the at least one susceptor and / or the at least one releaseable component.

7. A plurality of matrix particles according to any one of claims 1 to 6, wherein the at least one releaseable component is a single chemical substance, a combination of chemical substances, an organic chemical substance, and / or an inorganic chemical substance, and the at least one releaseable component comprises one or more catalysts, cocatalysts, coreactants, oxidizers, reaction inhibitors, accelerators, co-accelerators, fuels, explosives, or one or more combinations thereof.

8. A plurality of matrix particles according to any one of claims 1 to 7, wherein when the matrix material or the shell is subjected to deformation, dissolution, melting, expansion, contraction, rupture, plasticization, solvation, exposure to light, or one or more of these, at least one releaseable component is released.

9. A plurality of matrix particles according to any one of claims 1 to 8, wherein the particles are further chemically surface-modified through one or more chemical reactions, optionally comprising the at least one releaseable component, and optionally subsequently forming a partial or complete coating.

10. A plurality of matrix particles according to any one of claims 1 to 9, wherein the at least one releaseable component comprises a chemically functional monomer, the matrix material comprises a polymerization material, and optionally the matrix particles are coated with a polymerization coating, thereby having chemical functionality.

11. A plurality of matrix particles according to any one of claims 1 to 10, wherein one or more variable matrix materials comprises one or more of wax, polymethyl methacrylate (PMMA), other substituted acrylates, styrene, or one or more polymers or copolymers thereof.

12. A process for preparing a plurality of matrix particles according to any one of claims 1 to 11, using processes A, B, C, D, or a combination thereof, (A) includes emulsification, dispersion, and / or suspension polymerization, or (B) includes core-shell polymerization, or (C) is a copolymer, wherein the copolymerization step includes emulsification, dispersion, suspension polymerization, or a combination thereof. (D) is the following process: (i) A step of coating polymer microparticles with a material containing a susceptor and a releaseable component, (ii) A step of encapsulating microparticles in which a susceptor and releaseable components are embedded with a monomer material, oligomer material, or polymer material, and / or (iii) A step of fusing the susceptor and the releaseable component, and (iv) A process comprising the step of sealing the susceptor and the releaseable components in external pores on the surface of a porous microsphere or internal pores within a core.

13. A process for influencing a chemical reaction, or a process for releasing at least one releaseable component from a plurality of matrix particles, (i) To provide a bulk reaction mixture, (ii) To provide the matrix particles according to claims 1 to 11, (iii) Incorporating the plurality of matrix particles into the bulk reaction mixture, (iv) Optionally, incorporate the plurality of matrix particles into the bulk reaction mixture, and bombard the bulk reaction mixture with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once to thermally activate the susceptor components embedded in the matrix particles. The bulk reaction mixture containing the plurality of matrix particles is heated, Mechanically polishing the bulk reaction mixture containing the plurality of matrix particles, or A process that includes combinations of those.

14. A plurality of matrix particles according to any one of claims 1 to 11, wherein the CNTs are incorporated into the matrix particles by the process described in claim 12.

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

16. The whole or part of it (i) A polymerizable composition of at least one chemical substance or several polymerizable compositions, (ii) a reinforced composite article; (iii) Laminated articles, (iv) rigid laminated articles, (v) a flexible laminate article; (vi) foam, or (vii) an article prepared as described in claim 12, which is a combination thereof.

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

18. A plurality of matrix particles according to any one of claims 1 to 11 and 14, wherein the releaseable component is a catalyst selected from the group consisting of transition metal complexes; transition metal alkoxides; stannous(II) bis(2-ethylhexanoate); carboxylates, alkoxides, and complexes of stannous, bismuth, zinc, and titanium; blockized superacids; dodecylbenzenesulfonic acid; dinonylnaphthalenesulfonic acid; N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine; organic bases; 1,8-diazabicyclo[5.4.0]undeca-7-ene; 1,5-diazabicyclo[4.3.0]nonene-5); (1,4-diazabicyclo2.2.2-octane); 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 to form one or more matrix particle layers.

20. A precursor, intermediate, or final monomer composition, oligomer composition, or polymer composition comprising a plurality of matrix particles as described in any one of claims 1 to 11 and 14, wherein the composition is prepared by solid-phase polymerization or 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 include carbon nanotubes, and the carbon nanotubes are coated on 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 by a fusion process.

23. A plurality of 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. A plurality of 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 as described in any one of claims 1 to 11, 14, and 18, wherein the composition is optionally prepared from a functionalized polymer formulation, and optionally prepared as a reactive blend with a non-reactive polymer or oligomer.

26. A process that influences a chemical reaction, (i) To provide a bulk reaction mixture, (ii) To provide a plurality of matrix particles according to any one of claims 1 to 11, 14, and 18, (ii) The plurality of matrix particles are incorporated into the bulk reaction mixture, and the bulk reaction mixture is struck 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 components embedded in the matrix particles. The bulk reaction mixture containing the plurality of matrix particles is heated, Mechanically polishing the bulk reaction mixture containing the plurality of matrix particles, or combinations of those, including The bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for solid-phase polymerization. The bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive hot melt formulation. The bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a reactive blend with a non-reactive polymer or oligomer, or A process wherein the bulk reaction mixture is a monomer composition, oligomer composition, or polymer composition that is a precursor or intermediate for a functionalized polymer formulation.

27. A process for increasing the overall fill volume of a bulk physically or chemically variable composition of CNTs by any one of the prior claims 29.

28. A process for maintaining lower viscosity when adding at least one additive to a bulk physically or chemically variable composition, comprising: incorporating the at least one additive as at least one releaseable 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 process for increasing the overall filling amount of additives in a bulk physically or chemically variable composition, (i) To provide a composition of the bulk that can be physically or chemically altered, (ii) Incorporating at least one of the additives as a releaseable component into the plurality of matrix particles according to claims 1 to 11, 14, and 18, (ii) Incorporating the plurality of matrix particles into the bulk physically or chemically variable composition, and thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk physically or chemically variable composition with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once. The bulk physically or chemically modifiable composition containing the plurality of matrix particles is heated, Mechanically polishing the bulk, physically or chemically modifiable composition containing the plurality of matrix particles, or combinations of those, including The process wherein the bulk physically or chemically modifiable composition is optionally a monomer composition, oligomer composition, or polymer composition, or a combination thereof, of a precursor or intermediate for reactive hot melt formulations, adhesives, coatings, or composites.

30. A process for maintaining lower viscosity when adding at least one additive to a bulk physically or chemically modifiable composition, (i) A step of providing a physically or chemically modifiable composition of the bulk, (ii) A step of incorporating at least one additive as a releaseable component into a plurality of matrix particles according to claims 1 to 11, 14, and 18. (ii) Incorporating the plurality of matrix particles into the bulk physically or chemically variable composition, and thermally activating the susceptor components embedded in the matrix particles by bombarding the bulk physically or chemically variable composition with RF radiation of at least one frequency and / or MW radiation of at least one frequency at least once. The bulk physically or chemically modifiable composition containing the plurality of matrix particles is heated, A step of mechanically polishing the bulk, which is physically or chemically modifiable, including the plurality of matrix particles, or combinations of those, including The process wherein the bulk physically or chemically modifiable composition is optionally a monomer composition, oligomer composition, or polymer composition, or a combination thereof, of a precursor or intermediate for reactive hot melt formulations, adhesives, coatings, or composites.

31. A plurality of matrix particles according to any one of claims 1 to 11 and 14, wherein the releaseable component is a catalyst for curing, polymerizing, or reacting acrylates, silane-terminated polymers, hydrolysis, condensation catalysts, isocyanate trimerization, 1K moisture-curable isocyanates, melamine crosslinked systems, 2K polyurethanes, 1K blocked isocyanate-based polyurethanes, epoxy, esterification, and transesterification.

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