Hybrid epoxy methacrylate

Abstract

A two-component hybrid epoxy material comprising a first component including (i) at least one epoxy resin, and (ii) at least one oxidizing agent, a second component including at least one acidic phosphorus material without olefinic unsaturation, wherein at least one olefinic unsaturated moiety is present in the first component or the second component or both, and wherein upon mixing the first and second components a polymeric material comprising a reactive continuous phase is formed.

Description

Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025HYBRID EPOXY METHACRYLATECLAIM OF PRIORITY

[0001] This application claims the benefit of the priority date of United States Provisional Application Serial No. 63 / 688,558, filed on August 29, 2024. Tire contents of that application are hereby incorporated by reference herein in their entirety and for all purposes.FIELD

[0002] The present teachings relate generally to a two-component hybrid epoxy material . More specifically, the present teachings relate to a first and second component that upon mixing with one another react to form a polymeric material comprising a reaction product of an epoxy and at least one olefinic unsaturated moiety.BACKGROUND

[0003] In both the consumer and industrial markets, two-component, polymerizable materials are commonly used in a variety of manners including structural repairs, bonding, scaling, encapsulating, casting, and reinforcing. It has long been known that phosphoric and phosphonic acid can be used to rapidly cure epoxy resins. However, due to the exceedingly fast reaction rate between the tri-fiinctional acids and di- functional or greater epoxy resins, little commercial success had been found with this polymerization technique. As described in United States Patent No. 10,550,220, success has been found in polymerizing epoxy resins with phosphoric or phosphonic acid esters. The combination of increased molecular weight of the acidic phosphorous component in conjunction with reduction in available acidic hydrogens reduces tire reactivity of the material with epoxy resins to the point where they may be used for a wide range of applications.

[0004] Acidic phosphorous materials have also long been used as adhesion promoters in a wide range of polymerization platforms. This gives the curative a dual purpose of both building a polymeric network, as well as promoting adhesion to a variety of substrates including, but not limited to metals, glass, ceramic, and cementitious materials. While epoxy-acidic phosphorous polymers have many advantages, formulation strategies for property modification are constantly explored.

[0005] Using epoxy in methacrylate adhesives has been commonplace for many years, particularly in methyl methacry late structural adhesives. These two-component systems often use epoxy as a carrier for the free radical initiator, typically benzoyl peroxide. As these systems typically employ 2-hydroxyethyl methacrylate phosphate ester as an adhesion promoter, incidental esterification of the epoxy carrier occurs, allowing the epoxy to react into the methacrylate polymer. This provides improved properties over a non- reactive plasticizer carrier. However, the epoxy component typically only comprises approximately 2 - 25 wt% of the continuous phase of the composition, whereas the free radical polymerizable portion typicallyAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 comprises 50 - 100 wt% of the continuous phase of the composition. At this epoxy concentration, it is believed that a long epoxy-acid phosphorous polymer chain is unable to form prior to vitrification of the (meth)acrylate network.

[0006] United States Patent Publication No. 2020 / 0002587 describes an Acrylic-Epoxy Hybrid Adhesive. The uniqueness of this material lies in the use of a blend of a high Tg and low Tg urethane (meth)acrylate to generate high peel strength. The methacrylate portion of the provided example material is approximately 48% by weight, whereas the epoxy portion of the material is approximately 9% by weight when mixed.

[0007] It may thus be desirable to employ hybridization of epoxy with a free radical polymerizable species such as an acrylate or methacrylate functional material in combination with phosphoric or phosphonic acid esters as curatives. Such hybridization and cure mechanisms may allow for modification of many properties including, but not limited to viscosity, glass transition temperature (Tg), gel time, and adhesion to polymeric substrates.SUMMARY

[0008] A composition of a two-component, polymerizable epoxy methacrylate hybrid material is disclosed herein. The first component comprises an epoxy resin or blend of epoxy resins, preferably with an average epoxy functionality of at least about 1.8. The second component comprises an acidic phosphorous material with or without olefinic unsaturation.

[0009] Preferably, the second component comprises an acidic phosphorous material or blend of acidic phosphorous materials including, but not limited to phosphoric acid, phosphonic acid and / or their esters thereof in an amount to substantially polymerize the epoxy resin.

[0010] At least one of the first or second component contains an olefinic unsaturated species (moiety) (e.g., an acrylate and / or methacrylate functional material). Preferably, the olefinic unsaturated moiety is capable of undergoing free radical polymerization.

[0011] The first component includes at least one oxidizing agent or free radical initiator. The first and the second component are separate from one another. When the first and second component are mixed with one another, a reactive continuous phase is formed. Preferably, the epoxy resin and acidic phosphorous materials shall comprise of at least about 50% of the reactive continuous phase by mass of resulting polymeric material.

[0012] Three preferred embodiments can be distinguished from one another. They all have in common that the two-component hybrid epoxy material comprises- a first component including (i) at least one epoxy resin, and (ii) at least one oxidizing agent (free radical initiator); andAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025- a second component including at least one acidic phosphorus material.

[0013] Further, they all have in common that at least one olefinic unsaturated moiety is present in the first component or the second component or both, and that upon mixing the first and second component with one another, a reactive continuous phase is formed.

[0014] According to the first of the three embodiments, tire at least one acidic phosphorus material that is contained in the second component is without olefinic unsaturation.

[0015] According to the second of the three embodiments, the at least one acidic phosphorus material that is contained in the second component is with olefinic unsaturation; and the at least one epoxy resin and the at least one acidic phosphorous material is present in a total amount of at least about 50% of tire reactive continuous phase by mass.

[0016] According to the second of the three embodiments, the second component includes two acidic phosphorous materials, namely (i) at least one acidic phosphorus material without olefinic unsaturation, and (ii) at least one acidic phosphorus material with olefinic unsaturation; and the at least one epoxy resin and one or more of tire at least one acidic phosphorous material is present in a total amount of at least about 50% of the reactive continuous phase by mass.

[0017] The first component of the composition is an epoxy resin or blend of epoxy resins preferably having an average molecular epoxide functionality of at least about 1.8. Said blend of resins may be composed of cyclic epoxy resins, such as Bisphenol A diglycidyl ether, linear epoxy resins, such as 1.6-hexanediol di- glycidyl ether, or an epoxy resin containing a blend of cyclic and linear components, such as an epoxy adduct of dimer fatty acid, as well as blends thereof. The reactive epoxide group may be terminal in nature, such as is in bisphenol A diglycidyl ether, epoxidized seed oils, such as epoxidized linseed oil, although other epoxide functionalities can be contemplated.

[0018] The second component comprises of an acidic phosphorous material or blend of acidic phosphorous materials. Tire second component comprises an acidic phosphorous material with or without olefinic unsaturation. Preferred acidic phosphorous materials or blends of acidic phosphorous materials include, but are not limited to phosphoric acid, phosphonic acid and / or their esters thereof in the amount to substantially polymerize the epoxy resin. Such esters include, but are not limited to, epoxy acid phosphate esters, alcohol acid phosphate esters, epoxy acid phosphonate esters, or alcohol acid phosphonate esters. Tire acidic phosphorous material may have one acidic phosphorous moiety such as butyl acid phosphate, or contain two or more acidic phosphorous moieties, such as in polyethylene glycol diphosphate or as in polymers or copolymers of 2-hydroxyethyl methacrylate acid phosphate. The acidic phosphorous material may also include organophosphonates such as vinyl phosphonic acid.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0019] At least one of the first and second component shall contain an olefinic unsaturated moiety. Such materials containing an olefinic unsaturated moiety include, but are not limited to acrylates, methacrylates, allylics, vinylics, and other various unsaturated components.

[0020] At least one component shall contain an oxidizing agent that is preferably capable of generating a free radical (free radical initiator). Said oxidizing agent is preferably used for the polymerization of the olefinic unsaturated moiety. Said oxidizing agent may contain peroxy, hydroperoxy, azo, or sulfonyl chloride functionality, however, other radical generating sources may be applicable and can be selected by those skilled in the art. For the purpose of the specification, the terms "oxidizing agent" and "free radical initiator" are used interchangeably.

[0021] Radical initiation may be generated through a variety of means. Heat may be used to decompose the oxidizing agent to initiate free radical polymerization. Said heat may be from an external source or from an internal source, such as an exothermic reaction upon mixing the two components. Ultraviolet radiation may be used to polymerize the olefinic unsaturated moiety using appropriate initiators known to those skilled in the art. Reducing agents including, but not limited to, N,N-dimethyl-para-toluidine, aniline, or N,N-diethyl-para-toluidine may be used to initiate free radical polymerization with appropriate oxidants known to those skilled in the art. Likewise, metals, metallocenes, metal salts and other organometallic catalysts may be employed to generated a free radical with an appropriate oxidant.

[0022] The teachings herein arc directed to a two-component hybrid epoxy material comprising a first component including at least one epoxy resin and at least one oxidizing agent, a second component including at least one acidic phosphorus material without olefinic unsaturation, wherein at least one olefinic unsaturated moiety is present in the first component or the second component or both, and wherein upon mixing the first and second components with one another a reactive continuous phase is formed. Subsequently, a polymeric material is formed from the reactive continuous phase. Thus, upon mixing the first and second component with one another, finally a polymeric material is formed.

[0023] Preferably, curing of the at least one epoxy resin of the first component is induced by the at least one acidic phosphorus material of the second component. Preferably, a continuous epoxy-phosphate ester network is formed.

[0024] Preferably, polymerization of the at least one olefinic unsaturated moiety is induced by the at least one oxidizing agent of the first component.

[0025] Preferably, an interpenetrating polymer network is formed.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0026] Preferably, the two-component hybrid epoxy material consists of the first and second component of the two-component hybrid epoxy material. For the purpose of the specification, the tenn "reactive continuous phase" refers to the mixture of the first and second component of the two-component hybrid epoxy material. Preferably, the reactive continuous phase consists of the first and second component of the two- component hybrid epoxy material. Thus, the weight of the reactive continuous phase is preferably the sum of the individual weight of the first component plus the individual weight of the second component.

[0027] The at least one epoxy resin and at least one acidic phosphorous material may be present in an amount of at least about 50% of a reactive continuous phase by mass.

[0028] The at least one epoxy resin or blend of epoxy resins may have an average molecular epoxide functionality’ of at least about 1.8.

[0029] The reactive continuous phase may include a cross linked network of the first and second components. Said cross linked network of the first and second component may be formed upon mixing the first and second component with one another.

[0030] For the purpose of the specification, the terms "olefinic unsaturated moiety" and "olefinic unsaturation" are used interchangeably. Tire at least one olefinic unsaturated moiety may be selected from the group consisting of: acrylates, methacrylates, allylics and vinylics. Preferred acrylates include acrylic acid esters and amides. Preferred methacrylates include methacrylic acid esters and amides. Allylics carry at least one allyl group (-CH=CH2-CH=CH2). Vinylics carry’ at least one vinyl group (-CH=CH2).

[0031] The at least one olefinic unsaturated moiety may be monofunctional (i.e., comprise a single olefinic unsaturation).

[0032] The at least one olefinic unsaturated moiety may be difunctional (i.e., comprise two olefinic unsaturations).

[0033] The at least one olefinic unsaturated moiety may be polyfiinctional (i.e., comprise at least three olefinic unsaturations).

[0034] The oxidizing agent may generate a free radical polymerizing the at least one olefinic unsaturated moiety.

[0035] The oxidizing agent (free radical initiator) may be selected from the group consisting of peroxides, hydroperoxides, azo functional compounds, sulfonyl chloride containing compounds and photo sensitive radical initiators.

[0036] The oxidizing agent may be thermally decomposed, generating a radical species.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0037] The oxidizing agent may be decomposed at room temperature wherein the two-component hybrid epoxy material further includes an accelerator and or a catalyst generating a radical species.

[0038] Tire acidic phosphorous material may be selected from the group consisting of phosphoric acid, phosphonic acid and / or their esters, epoxy acid phosphate esters, alcohol acid phosphate esters, epoxy acid phosphonate esters, organo- phosphonates, alcohol acid phosphonate esters, and combinations thereof.

[0039] The acidic phosphorous material may include one acidic phosphorous moiety or contains two or more acidic phosphorous moieties. Typically, the acidity of the acidic phosphorous material relies upon the presence at least one hydroxyl group that is directly bonded to a phosphorous atom, i.e. not esterified. Preferably, tire phosphoric acid esters, phosphonic acid esters or phosphonate esters are monoesters or diesters.

[0040] The teachings herein are further directed to a two-component hybrid epoxy material comprising a first component including at least one epoxy resin, and at least one oxidizing agent or free radical initiator, a second component including at least one acidic phosphorus material with olefinic unsaturation, wherein upon mixing of the first and second components a polymeric material is fomied wherein the at least one epoxy resin and at least one acidic phosphorous material is present in an amount of at least about 50% of a reactive continuous phase by mass, and wherein upon mixing of the first and second components a continuous epoxy-phosphate ester network is formed.

[0041] The teachings herein are also directed to a two-component hybrid epoxy material comprising a first component including at least one epoxy resin, and at least one oxidizing agent, and a second component including at least one acidic phosphorus material without olefinic unsaturation and at least one acidic phosphorus material with olefinic unsaturation, wherein upon mixing of the first and second components a polymeric material is formed wherein the at least one epoxy resin and at least one acidic phosphorous material is present in an amount of at least about 50% of a reactive continuous phase by mass.DETAILED DESCRIPTION

[0042] Tire present teachings meet one or more of the above needs by the improved devices and methods described herein. The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the teachings, its principles, and its practical application. Those skilled in the art may adapt and apply the teachings in its numerous forms, as may be best suited to the requirements of a particular use. Accordingly, the specific embodiments of the present teachings as set forth are not intended as being exhaustive or limiting of tire teachings. The scope of the teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

[0043] Use of epoxy in methacrylate adhesives has been commonplace for many years, particularly in methyl methacrylate structural adhesives. These two-component systems often use epoxy as a carrier for the free radical initiator, typically benzoyl peroxide. As these systems typically employ 2-hydroxyethyl methacrylate phosphate ester as an adhesion promotor, incidental esterification of the epoxy carrier occurs, allowing tire epoxy to react into the methacrylate polymer. This provides improved properties or other effects over a non-reactive plasticizer carrier. However, the epoxy component typically only comprises approximately 2 - 25 wt% of the continuous phase of the composition, whereas the free radical polymerizable portion typically comprises 50 - 100 wt% of the continuous phase of the composition. United States Patent Publication No. 2010 / 0065210 teaches a two-component adhesive in which one component claims a methacrylate monomer, amine catalyst, an optional second catalyst, a reactive acid component, a free-radical inhibitor, and a second component that includes a resin component containing epoxy groups, a peroxide and a basic metal compound. The example of this patent demonstrates a material that is mixed 10 parts methacrylate component to 1 part epoxy and peroxide component.

[0044] Table 1 illustrates that in the absence of a free radical initiator, blends of methacrylate monomer, 2- HEMA phosphate, and epoxy resin require a critical concentration of acidic phosphate ester and epoxy resin to form a continuous epoxy-phosphate ester network.

[0045] Table 1. Critical Concentration of Epoxy -Phosphate Ester Constituents for Network Formation

[0046] In all instances outlined in Table 1, the liquid epoxy novolac resin and 2-HEMA phosphate reacted to form a gel material. However, in Samples 1 and 2, the cured epoxy and phosphate ester sank to the bottom of tire container and were unable to form a continuous network though the mixture. Conversely, the gel networks fonned from Samples 3-5 spanned the entire volume of the mixture.

[0047] Disclosed herein is a composition of a two-component, polymerizable epoxy methacrylate hybrid material. Tire first component comprises an epoxy resin or blend of epoxy resins, preferably with an average epoxy functionality of at least about 1.8. The second component comprises an acidic phosphorous materialAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 or blend of acidic phosphorous materials including, but not limited to, phosphoric acid, phosphonic acid and / or their esters thereof in an amount suitable to substantially polymerize the epoxy-containing component. At least one component must contain an olefinic unsaturated species (moiety) capable of undergoing free radical polymerization (e.g., an acrylate and / or methacrylate functional material). The first component contains an oxidizing agent (free radical initiator). When the first and second components are mixed, the epoxy resin and acidic phosphorous material shall comprise of at least about 45%, and preferably at least about 60% of the reactive continuous phase by mass. It is also possible that an oxidizing agent could be present in the second component, with or without presence of the oxidizing agent in the first component.

[0048] The first component of the composition is an epoxy resin or blend of epoxy resins, preferably having an average molecular epoxide functionality of at least about 1.8. The blend of epoxy resins may comprise one or more of cyclic epoxy resins, such as bisphenol A diglycidyl ether, linear epoxy resins, such as 1,6- hexanediol diglycidyl ether, or an epoxy resin containing a blend of cyclic and linear components, such as an epoxy adduct of dimer fatty acid, as well as blends thereof. The reactive epoxide group may be terminal in nature, such as is in bisphenol A diglycidyl ether, or along the backbone, although other epoxide functionalities can be contemplated. The epoxy resin is reactive through its epoxy functional groups. When the first and second component are mixed with one another, reaction of the epoxy functional groups is preferably induced by the at least one acidic phosphorous material. A cured epoxy resin is thus obtained, preferably a continuous epoxy-phosphate ester network.

[0049] The second component comprises an acidic phosphorous material or blend of acidic phosphorous materials including, but not limited to, phosphoric acid, phosphonic acid and / or their esters thereof in an amount sufficient to substantially polymerize the epoxy resin. Such esters include, but are not limited to, epoxy acid phosphate esters, alcohol acid phosphate esters, epoxy acid phosphonate esters, or alcohol acid phosphonate esters. Hie acidic phosphorous material may have one acidic phosphorous moiety, such as butyl acid phosphate, or contain two or more acidic phosphorous moieties, such as in polyethylene glycol diphosphate or as in polymers or copolymers of 2-hydroxyethyl methacrylate acid phosphate. The acidic phosphorous material may also include organophosphonates such as vinyl phosphonic acid.

[0050] At least one component shall contain an olefinic unsaturated moiety. Such materials include, but are not limited to, acrylates, methacrylates, allylics, vinylics, and other various olefinic unsaturated species (moieties). Said olefinic unsaturated moiety may be monofunctional in nature such as methyl methacry late, isobomyl acrylate, isobomyl methacrylate, tetrahydrofurfury 1 methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate caprolactone methacrylate, cyclohexyl acrylate, styrene, dimethylacrylamide, and the like. Alternatively, said component may be difiinctional or greater such as neopentyl glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A acrylate, pentaerythritol pentacrylate, trisisocyanurateAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 triacrylate. Said olefinic unsaturated material may contain secondary functional groups including, but not limited to, hydroxyl, hydroxide, carboxylic acid, amine, amide, imine, acid phosphate, and acid phospho- nates.

[0051] The second component of the composition may contain an acidic phosphorous material containing an olefinic unsaturated organic moiety. Such materials include, but are not limited to, 2-hydroxyethyl methacrylate phosphate monoester, 2-hydroxyethyl methacrylate phosphate diester, 2-hydroxypropyl methacrylate phosphate monoester, 4-hydroxybutyl acrylate phosphate monoester, or vinylphosphonic acid.

[0052] The first component contains an oxidizing agent preferably capable of generating a free radical (free radical initiator). The oxidizing agent may be used for the polymerization of the olefinic unsaturated moiety. The oxidizing agent may include, but is not limited to, benzoyl peroxide, tert-butyl peroxide, dicumyl peroxide, and the like. The oxidizing agent may be a hydroperoxide such as cumene hydroperoxide, or t-butyl hydroperoxide.

[0053] The oxidizing agent may also include materials with azo functionality. Such materials include but are not limited to azodicarbonamide, 2.2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2.2'-azo- bis(2-methylpropionamidine)dihydrochloride. and 4,4'-azobis(4-cyanovaleric acid).

[0054] The oxidizing agent may contain a sulfonyl chloride species. Such materials include, but are not limited to, tosyl chloride, mesyl chloride, and chlorosulfonated polyethylene.

[0055] The oxidizing agent may include photosensitive radical initiators. Such materials generate a radical species upon irradiation with ultraviolet or near ultraviolet light. Such materials include but are not limited to 1-hydroxy-cyclohexyl-phenyl-ketone, 1 -[4-(2 -hydroxyethoxy)-phenyl]-2-hydroxy-2 -methyl- 1-propane- 1-one, and trimethylbenzoyldiphenyl phosphine oxide.

[0056] Where appropriate, the oxidizing agent may be thermally decomposed to generate a radical species. The thermal energy may be provided from an external source, such as an oven or infrared heater, or internally as a result of reaction exotherm between the epoxy resin and acidic phosphorous material. Other methods of decomposition are possible and numerous and can be appropriately selected by those skilled in the art.

[0057] It is possible that the oxidizing agent (oxidant) can be decomposed at room temperature upon mixing of the two components when an appropriate accelerator, catalyst or blend of accelerators and / or catalysts is present. Such materials include, but are not limited to metallocenes, such as ferrocene, transition metals, transition metal salts, and amine functional materials such as N,N-dimethyl-para-toluidine. The accelerator, catalyst, or blend of accelerators and / or catalysts can be appropriately chosen from those known in the art.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0058] Preferred epoxy resins according to the disclosure include but are not limited to cyclic epoxy resins, linear epoxy resins, epoxidized seed oils, blends of cyclic and linear components, and blends thereof; preferably Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, epoxy novolac resins, 1,6-hexanediol diglycidyl ether, epoxidized linseed oil epoxy adducts of dimer fatty acid, or blends thereof.

[0059] Preferred oxidizing agents according to the disclosure include but are not limited to oxidizing agents containing contain peroxy, hydroperoxy, azo, or sulfonyl chloride functionality, and any combinations thereof; preferably tert-butyl peroxybenzoate (TBPB).

[0060] Preferred acidic phosphorous materials without olefinic unsaturation according to the disclosure include but are not limited to phosphoric acid, the esters thereof phosphonic acid, the esters thereof, and combinations thereof; preferably H3PO4, polyphosphoric acid, butyl acid phosphate, phosphate ester of glyc- idyl phenoxy ether, castor oil acid phosphate and any combinations thereof.

[0061] Preferred acidic phosphorous materials with olefinic unsaturation according to the disclosure include but are not limited to phosphoric acid esters with olefinic unsaturation, phosphonic acid esters with olefinic unsaturation, and combinations thereof; preferably the phosphate ester of 2-hydroxyethyl methacrylate (2-HEMA phosphate).

[0062] Preferred olefinic unsaturated moieties according to the disclosure include but are not limited to isobomyl methacrylate (IBOMA). and any combinations thereof.

[0063] One or more of the first or second components may contain a chelating agent. The chelating agent may be included in a system to strip transition or other active metal ions from one or both sides (components) of the two-component system. Tetrasodium EDTA is an example of one such chelating agent.

[0064] The first component, second component, or both may contain an antioxidant constituent. Said constituent may be incorporated into one or both components for a multitude of reasons including, but not limited to, improving shelf stability, extending gel time, and improving scorch resistance and moderating rate of reaction. Tire antioxidant may be deviated into two categories by those skilled in the art: aerobic and anaerobic stabilizers. Aerobic stabilizers function synergistically with atmospheric oxygen to create a stabilized radical species, whereas anerobic stabilizers, such as 4-hydroxy-TEMPO, will inhibit free radical polymerization independent of the presence of oxygen.

[0065] The materials of the present teachings may include dyes or pigments. These materials may be organic or inorganic in nature and may be present for purely aesthetic reasons or functional reasons. Alternate uses beyond the aesthetic include, but are not limited to UV blocking, reinforcing, corrosion resistance, and adhesion promotion. Examples of such materials include carbon blacks, TiO2, iron oxide-based pigments, zinc oxides, zinc phosphates, phthalocyanine blue, and toluidine red.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0066] Reinforcing components can be added to the resin component, the acidic component, or both. The reinforcing components may have a particle size of about 1 mm or less to maintain material flow during application. The reinforcing components may be organic or inorganic in nature. They may have a variety of shapes including spherical, cubic, platelet, needle, or fiber like. They may provide, but not be limited to, mix ratio control, reinforcing, rheological control, density control, dimensional stability or impact resistance to the polymer matrix. Examples of suitable reinforcing components include wollastonite, kaolin clay and other silicates, talc, ground rubber, filmed or precipitated silicas, fly ash, resinous dust and a variety of other minerals and micronized waste products.

[0067] In tire presence of acidic additives or curative materials, some reinforcing components may provide additional secondary effects. The use of metal carbonate materials releases carbon dioxide via a decomposition reaction upon contact with an acid. Tire generated gas from this reaction can be trapped during the polymerization process to create a foamed product. This may be useful for variable gap filling and improving adhesion, as w ell as counteracting the effect of shrinkage during the polymerization process.

[0068] One or more impact modifiers may also be added to the first component, second component, or both. Impact modifiers may be included to provide improved fracture toughness to the resin matrix and are characterized by having a soft portion of the molecule or polymer in which the glass transition temperature, or Tg, is less than at least about -20 °C and preferably less than -40 °C. Tire impact modifiers may be liquid in nature or solid in nature. The impact modifiers may or may not react into the binding resin matrix. Additionally. the impact modifiers may be either soluble or semi-soluble, as is the case for liquid butadiene or butadiene acrylonitrile rubbers, or insoluble in cases such as core-shell impact modifiers, ground tire rubber or other grades of size-reduced virgin rubber.

[0069] In some cases, ultraviolet absorbers (UVA) or hindered amine light stabilizers (HALS) may be added to the epoxy component to improve resistance to photooxidation due to long term exposure to ultraviolet light. UVA absorbing materials work by having strong light absorption peaks in the ultraviolet range of the electromagnetic radiation spectrum. Ulis reduces the probability of light in the ultraviolet spectrum being absorbed by the resin matrix and causing unwanted degradation. Unlike UVA materials. HALS do not absorb a substantial amount of UV light. Such materials react with photoradicals and convert them to less damaging peroxy species. Examples of UVA absorbing materials include, but are not limited to, poly(oxy-l,2-ethanediyl), .alpha.-[3-[3-(2H-benzotriazol-2-yl)-5- (l,l-dimethylethyl)-4-hydroxyphenyl]- 1 -oxopropyl] -.omega. -hydroxy and 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol. Examples of HALS include, but are not limited to, bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and methyl 1,2,2,6.6-pen- tamethyl-4-piperidyl sebacate.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0070] In certain instances, surfactant type materials may be added to tire first component, second component or both, with varying functions including substrate and reinforcing component wetting, viscosity reduction, air release, and defoaming. Surfactants lower surface tension and aid in wetting, which is the process of displacing the air entrained within the micropores of a material, allowing for improved interaction of the resin matrix with the bonding substrate. This can result in improved adhesion of the resin matrix to the substrate.

[0071] In certain embodiments, diluents and plasticizing materials may be added to the first component, second component, or both. These materials are typically of low molecular weight and may or may not react into the resin matrix. Such materials may be added to reduce viscosity, improve ductility or reduce stiffness of the resin matrix, and / or to fine tune the mix ratio of tire reactive components when dispensed from a fixed volume, 2K cartridge.

[0072] In certain embodiments, dehydrating the first component, second component, or both may be advantageous. Dehydration may occur through both chemical reaction and by means of entrapment. Chemical dehydration is a means of which an additive chemical may react with the water entrained in the continuous phase of either tire resin or acid system, resulting in a material that is chemically different than the starting additive. Chemical dehydration agents include, but are not limited to, isocyanates, and more specifically p- toluenesulfonyl isocyanate, oxazolidines, silanes, specifically vinyl trimethoxy silane, organic acid anhydrides. such as maleic anhydride, inorganic acid anhydrides such as polyphosphoric acid, phosphorous pentoxide, and group 2 metal oxides, such as calcium oxide. This list of materials is to be considered to be conceptually representative and is not a fully inclusive list.

[0073] Alternatively, physical entrapment of the water may also be used to remove water entrained in either the first component, second component, or both. One such method is crystal lattice confinement, in which a partially or fully dehydrated crystalline salt is added to the material and the water is absorbed by the crystal lattice. Examples of such materials include, but arc not limited to, anhydrous magnesium sulfate, anhydrous copper sulfate, and calcium sulfate hemihydrate. An additional method of water entrapment is by incorporating highly hydrophilic particles into the continuous phase of tire system. Such materials adsorb moisture and will not readily desorb moisture back into the continuous phase. Examples of such materials include but are not limited to molecular sieves, zeolites, silica gel, and sodium polyacrylate.

[0074] In certain embodiments, use of solid, high molecular weight resins may be beneficial for enhancing the physical properties of the cured resin matrix. These materials may be high or low modulus in nature, depending on the property or properties that are of interest. Physical properties that may be modified via use of solid resins include, but are not limited to, compressive modulus, tensile modulus, tensile stress, tensile elongation, environmental exposure resistance, and chemical resistance. Examples of such materialsAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 include, but are not limited to, (meth)acrylate polymers and copolymers, phenoxy resins, urethane resins, polyvinyl alcohols, polyvinyl butyrals, ethylene vinyl acetates, cellulosic resins, polychloroprenes, polyisoprenes, and SBS block copolymers.

[0075] Example 1:

[0076] Example 1 illustrates the use of a monofunctional methacrylate, isobomyl methacrylate (IBOMA), as the olefinic unsaturated species (moiety) to copolymerize in a phosphate ester-cured epoxy system. Example 1 illustrates an improvement in onset glass transition temperature (Tg), derived from the DMA storage modulus thermal sweep, and / or storage modulus retention at 80 °C when utilizing both acidic phosphate esters, which contain olefinic unsaturation in the ester group, and those which do not. The olefinic unsaturated phosphate ester is 2-hydroxyethyl methacrylate phosphate. The phosphate ester curative without olefinic unsaturation is butyl acid phosphate. Hie R=1 designation for each of the acidic phosphate esters indicates that the synthesis of the ester is performed with a ratio of 1 alcohol per phosphorous atom. The peroxide curative, tert-butyl peroxybenzoate (TBPB), is added at 2% of the level of IBOMA.

[0077] Samples are prepared in accordance with Tables 2, 4, and 6 below (amounts are by mass). A theoretical Acid:Epoxy ratio of 0.727: 1 is used for all samples. All samples are speed mixed at 2500 rpm for 20 seconds and allowed to cure at ambient temperature overnight. Following the ambient cure, all samples are baked at 325 °F (163 °C) for 1 hour. Tg and storage modulus are measured using a Q800 DMA with a temperature ramp rate of 5° C / minutc and oscillation rate of 1 Hz.

[0078] Table 2. Saturated Phosphate Ester Epoxy Matrix with Isobomyl Methacrylate

[0079] Table 3. Performance of Saturated Phosphate Ester Hybrid MaterialsAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0080] Table 3 illustrates the performance of a mono-functional methacrylate monomer, isobomyl methacrylate (IBOMA), when used as a hybridizing polymerizable species in an acidic phosphorous cured epoxy resin material without olefinic unsaturated species (moiety) in the acidic phosphorous-epoxy network. As such, the resulting co-polymerized materials result in a primarily interpenetrating network. Due to the presence of TBPB in Table 3, weight percent totals do not add up to 100%.

[0081] Sample US-1 is an IBOMA-free control sample of the acid phosphate cured sample. As illustrated in samples US-2 through 5, increasing concentrations of IBOMA result in a continuously decreasing storage modulus of the hybrid polymer. However, in US-6, the storage modulus returns to a value near that of the control. Additionally, while US-6 has a lower storage modulus (E ) and Tan Delta Tg than the control material, there was a retention of storage modulus at 80 °C nearly an order of magnitude greater than that of the control material. Without being bound to any theory, it is believed the IBOMA behaves more as a plasticizer in samples US-2 through US-5, as the methacrylate concentration is too low to fomr a well polymerized network, until a critical concentration of methacrylate is reached in US -6.

[0082] Table 4 outlines compositions in which there is partial olefinic unsaturation in the acidic phosphorous-epoxy network. In this instance, the phosphate ester of 2-hydroxyethyl methacrylate (2-HEMA) is used as both a chain extender for the epoxy network, and crosslinker for the methacrylate network.

[0083] Table 4. Blend of Saturated and Unsaturated Phosphate Esters with Isobomyl Methacrylate

[0084] Table 5. Performance of Blended Saturated and Unsaturated Phosphate Ester Hybrid MaterialsAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0085] As illustrated in Table 5, compositions containing partial unsaturation in tire acidic phosphorous- epoxy network experience an immediate improvement in both E’ and Tan Delta Tg, as well as storage modulus at both 25 °C and at 80 °C when IBOMA is added to the composition. Continuous improvement in storage modulus retention at 80 °C is witnessed with increasing concentrations of IBOMA. The 2-HEMA phosphate ester molecule enables covalent linkage of a methacry late and epoxy side of an adhesive system, by containing an unsaturated group and acidic functionality. This allows for higher Tg thermosets and greater retention of mechanical properties at 80 °C. Total weight percentages of the (meth)acrylate network and acidic phosphorus-epoxy networks add to an amount greater than 100% due to the 2-HEMA phosphate forming covalent bonds in both networks.

[0086] Table 6 outlines compositions in which only the acidic phosphate ester of 2-HEMA is utilized to extend the acid phosphorous-epoxy network, and Table 7 describes the thermo-mechanical properties of the compositions described in Table 6.

[0087] Table 6. Unsaturated Phosphate Esters with Isobomyl Methacrylate

[0088] Table 7. Performance of Unsaturated Phosphate Ester Hybrid MaterialsAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0089] As illustrated in Table 7. compositions containing solely acidic molecules with olefinic unsaturation (no butyl acid phosphate), in the acidic portion of the acidic phosphorous-epoxy network, experience further improvements in both E’ and Tan Delta Tg, as well storage modulus at both 25 °C and at 80 °C when IBOMA is added to tire composition. Continuous improvement in storage modulus retention at 80 °C is witnessed with increasing concentrations of IBOMA, from 9.48% retention for US-19 (no IBOMA) up to 92.36% retention for US-22 (44.5 wt% IBOMA). Direct comparisons may be made between US-15 vs US- 20 and US-17 vs US-21, as they respectively utilize the same A side (first component) (resins with differing levels of IBOMA) but go from a blend of butyl acid phosphate and HEMA phosphate to purely HEMA phosphate. When comparing samples US-15 to US-20, improvements in both Tg and storage modulus at 80 °C arc observed with higher concentrations of the acidic phosphate ester of 2-HEMA. The Tg (tan delta) increases from 93 °C to 111 °C and the 80 °C storage modulus increases from 418 MPa to 1123 MPa. When comparing samples US-17 to US-21, the Tg (tan delta) increases from 95 °C to 117 °C and the 80 °C storage modulus increases from 704 MPa to 1341 MPa. Without being bound to any theory, it is believed this is due to the higher methacrylate crosslinking potential of an epoxy network fully extended with 2-HEMA phosphate ester versus networks extended with only a portion of the phosphate esters containing olefinic unsaturated functionality, i.c. a blend of butyl acid phosphate and 2-HEMA phosphate esters.

[0090] Example 2:

[0091] Example 2 illustrates the use of a difunctional acrylate, bisphenol A (ethoxylated)4 diacrylatc. under the trade name Miramer M240, as the olefinic unsaturated species (moiety) to copolymerize in a phosphate ester-cured epoxy system. Example 2 illustrates an improvement in either, or both, onset glass transition temperature (Tg) or storage modulus retention at 80°C, when utilizing both acidic phosphate esters which contain olefinic unsaturation functionality and those which do not. The olefinic unsaturated phosphate ester used is 2-hydroxyethyl methacrylate phosphate. The phosphate ester curative without olefinic unsaturation is butyl acid phosphate. The peroxide curative, tert-butyl peroxybenzoate (TBPB), is added at 2% of the level of M240.

[0092] Samples are prepared in accordance with Tables 8, 10, and 12 below. A theoretical Acid:Epoxy ratio of 0.727 : 1 is used for all samples. All samples are speed mixed at 2500 rpm for 20 seconds and allowed to cure at ambient temperature overnight. Following the ambient cure, all samples are baked at 325 °F (163 °C) for 1 hour. Tg and storage modulus are measured using a Q800 DMA using a temperature ramp rate of 5°C / min and an oscillation rate of 1 Hz.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0093] Table 8 outlines compositions in which only the acidic phosphate ester of 1 -butanol is utilized to extend the acid phosphorous-epoxy network, and Table 9 describes the thermo-mechanical properties of the compositions described in Table 8.

[0094] Table 8. Saturated Phosphate Ester Epoxy Matrix with Bisphenol A (Ethoxylated)4 Diacrylate

[0095] Table 9. Performance of Saturated Phosphate Ester Hybrid Materials with Bisphenol A (Ethoxylated)4 Diacrylate

[0096] Table 9 demonstrates that at a lower concentration of diacrylate component (US-23), and no unsaturation in the epoxy-phosphate ester backbone, the diacrylate component acts as a plasticizer, resulting in a lower storage modulus and Tg. However, the bisphenol A (ethoxylated)4 diacrylate shows an improvement in both ambient and 80 °C storage modulus at a lower concentration than when using IBOMA. Using only the saturated butyl acid phosphate and IBOMA, the 80 °C storage modulus does not increase until US-6 (see Table 3), which is 42 wt% IBOMA, and the ambient storage modulus is still less than that of US-1 made without IBOMA. Using only tire saturated butyl acid phosphate and Miramer M240, the 80 °C storage modulus begins increasing in US-24 with 36.8 wt% M240 and the ambient storage modulus has increased to 1506 MPa versus 1237 MPa (US-1). Without being bound to any theory, it is believed that a difunctional and greater olefinic unsaturated moieties’ ability to form crosslinked homopolymers, rather than thermoplastics, would allow for a continuous or semi-continuous network to be formed at a lower concentrationAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 when unable to react into the epoxy-phosphate ester network. This is due to tire lack of unsaturation in the butyl acid phosphate ester.

[0097] Analogous to Table 4, Table 10 outlines compositions in which there is partial olefinic unsaturation in the acidic phosphorous-epoxy network. In this instance, the phosphate ester of 2-hydroxyethyl methacrylate (2-HEMA) is used as both a chain extender for the epoxy network, and crosslinker for the methacrylate network. Table 11 describes the thermo-mechanical properties of the hybrid networks formed by the compositions outlined in Table 10.

[0098] Table 10. Blend of Saturated and Unsaturated Phosphate Esters with Bisphenol A (Ethoxylated)4 Diacrylate

[0099] Table 11 . Performance of Blended Saturated and Unsaturated Phosphate Ester Hybrid Materials with Bisphenol A (Ethoxylated)4 Diacrylate

[0100] As outlined in Table 11, all additions of M240 result in improved onset Tg (about 15°C), ambient storage modulus, and 80 °C storage modulus when compared to tire US-13 control. Furthermore, comparing US-23 to US-25 with US-29 to US-31 respectively, a blend of unsaturated (HEMA phosphate ester) and saturated (butyl acid phosphate ester) esters shows significant improvement in properties over the purely saturated phosphate ester system. US-29 to US-31 show onset Tg of at least 20 °C higher with the addition of HEMA phosphate ester to the B side (second component), at vary ing levels of Miramer M240. US-31Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 has an 80 °C storage modulus of217 MPa, while the comparable US-25 is only 18 MPa without the HEMA phosphate ester, despite the addition of 46 wt% M240 to the A side (first component). These improvements are shown when an olefinic unsaturated phosphate ester, which can react with both the epoxy resin and diacrylate resin, is present in the epoxy-phosphate ester network.

[0101] Table 12 outlines compositions in which only the acidic phosphate ester of 2-HEMA is utilized to extend the acid phosphorous-epoxy network. In this instance, the phosphate ester of 2-hydroxyethyl methacrylate (2-HEMA) is used as both a chain extender for the epoxy network and a crosslinker for the methacrylate network. Table 13 describes the thermo-mechanical properties of the compositions described in Table 12.

[0102] Table 12. Unsaturated Phosphate Esters with Bisphenol A (Ethoxylated)4 Diacrylate

[0103] Table 13. Perfonnance of Unsaturated Phosphate Ester Hybrid Materials with Bisphenol A (Ethoxylated)4 Diacrylate

[0104] As described in Table 13, onset Tg improved by at least 18 °C in every' instance where bisphenol A (etlioxylated)4 diacrylate is added to a 2-HEMA acid phosphate ester cured epoxy network. Additionally, the ambient storage modulus and 80 °C storage modulus were both greatly improved for all samples (US- 32 to US-34) containing the bisphenol A (ethoxylated)4 diacrylate when compared to the control material (US-19). Furthermore, comparing US-32 to US-34 with US-29 to US-31 respectively, the pure unsaturated HEMA phosphate ester system shows significant improvement in properties over the blend of unsaturatedAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025(HEMA phosphate ester) and saturated (butyl acid phosphate ester) esters. The onset Tg for the unsaturated ester systems is increased by at least 15 °C, and the 80 °C storage modulus is increased by up to 860% (US- 32 vs US-29) due to the increased level of 2-HEMA phosphate and greater covalent bonding between the (meth)acrylate and epoxy components of the adhesive.

[0105] Example 3 - Room Temperature Catalyzed Methacrylate and Epoxy-Phosphate Ester Hybrid for Thin Bond Line Performance

[0106] Example 3 illustrates the use of an epoxy-phosphate ester network copolymerized with an olefinic unsaturated moiety' via room temperature free radical initiation. Example 3 demonstrates overlap shear performance when hybridizing an epoxy-phosphate ester network with a network derived from an olefinic unsaturated moiety with an appropriate free radical generating species.

[0107] All A-side (first component) constituents except for the Benox B-50 106 are mixed under vacuum via a SpeedMixer® in accordance with Table 14 until all materials are dispersed. The Benox B-50 106 is then added and mixed under vacuum until dispersed. B-side (second component) compositions are mixed with the following process. Polyphosphoric acid and Ecotrion H2000 are mixed at 2000rpm for 6 minutes via a SpeedMixer® in amounts outlined by Table 14. This mixture is allowed to sit overnight to react. The remaining B-side (second component) constituents are added and mixed under vacuum via a SpeedMixer®.

[0108] In said compositions, the Benox B-50 106 is a 50% benzoyl peroxide paste used as a free radical source. N,N-dimethyl -para-toluidine is a polymerization catalyst. The Naxonac HP 1000 is a commercially available 2-HEMA phosphate and is used as the only source of olefinic unsaturation.

[0109] Table 14. Compositions for Comparing Thin Bond Line Performance of Hybrid Adhesives with and without a Free Radical SourceAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0110] For formulations US-35 and US-36, parts A and B are respectively used to fdl 200mU 2: 1 fixed volume cartridge. Each sample is dispensed through a 10-24 helical static mixer for testing. Overlap shear samples are prepared with 25.4 mm x 101.6 mm test coupons with a 12.7 mm overlap and 0.25 mm bondline. Samples are cured for both 24 and 120 hours at ambient temperature prior to testing Overlap shear samples are tested with a crosshead speed of 10 mm / minute.

[0111] Table 15. Thin Bond Tine Performance of US-35 and US-36

[0112] As outlined in Table 15, sample US-35, containing the benzoyl peroxide free radical generator, has substantially higher overlap shear values than US-36, on both cold rolled steel (8.6 MPa vs 5.3 MPa) and EG60 high strength steel (4.4 MPa vs 1.1 MPa) after 24 hours of curing at ambient temperature. This indicates that the free radical source is polymerizing the methacrylate bonds of the 2-HEMA phosphate, allowing the system to reach a greater extent of cure at 24 hours compared to the acid phosphate-epoxy network alone. This is more evident after 120 hours of ambient cure where US-35 substantially outperforms US-36 on EG60 high strength steel (13.3 MPa vs 6.1 MPa), 6061 aluminum (17.4 MPa vs 12.2 MPa), and cold rolled steel (20.7 MPa vs 13.2 MPa).

[0113] Example 4:

[0114] Example 4 illustrates the use of an olefinic unsaturated moiety as a reactive diluent with improved physical properties over an epoxide functional reactive diluent. This example also illustrates the use of a reaction exotherm triggering the thcnnal decomposition of a peroxide species to initiate free radical curing.

[0115] Formulations in Table 16 are mixed under vacuum via a SpeedMixer®. Fonnula US-37 is representative of a high-strength foaming material. Formula US-38 represents a high-strength foaming materialAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025 in which some of the high viscosity liquid epoxy functional resins, Kane Ace™ MX-257 and YDPN-630, are partially replaced by an olefinic unsaturated reactive diluent, IBOMA, and its curative Luperox® P (TBPB). Formula US-39 represents a high-strength foaming material in which the high viscosity liquid materials are partially replaced by 1,4-cyclohexanedimethanol diglycidyl ether under the trade name of KF EPIOL-DE204.

[0116] Compositions are added to 2: 1 fixed volume 2K cartridges and were filled with parts A and B respectively. 130 grams are dispensed through a 10-24 helical static mixer into a 400 mL polypropylene beaker and allowed to cure for at least 24 hours. Physical properties and reactivity of the resulting compositions are described in Table 17.

[0117] Table 16. Compositions for Comparing Viscosity Reduction with Performance

[0118] Table 17. Properties of Reactive Diluent Containing MaterialsAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025

[0119] As shown in Table 17, both IBOMA (US-38) and DE204 (US-39) are effective diluents for the epoxy constituent, with IBOMA having a greater effect on viscosity reduction. However, with similar viscosity reduction of the base formulation, US-38 provides a 30 °C improvement in onset Tg over US-39. US- 38 shows a substantially higher ambient storage modulus compared to US-39 at a similar level of expansion. US-38 retains 55% of its storage modulus at 80 °C, whereas US-39 only retains 1.6% of its storage modulus at the same temperature. Sample US-37 was too viscous to dispense through a static mixer. As seen in previous examples, adhesives with unsaturated resins, such as IBOMA, in tire A-side (first component) show' superior mechanical properties at elevated temperatures, especially with unsaturated phosphate ester curing agents, such as 2-HEMA phosphate ester, in the B-side (second component).

[0120] Example 5:

[0121] Example 5 illustrates the use of both peroxide and azo free radical sources in a composition comprising of materials with secondary unsaturation. In said example, the does not contain any vinyl or (meth)acrylate moieties. such as 2-HEMA phosphate ester, like those described in previous examples.

[0122] Compositions described in Table 18 are mixed under vacuum via a SpeedMixer® and used to fill 2: 1 fixed volume cartridges A:B respectively. Compositions are dispensed through a 10-24 helical type static mixer to form a 4mm thick plaque and cured for 24 hours prior to testing. Once cured, tensile dogbone samples are cut and tested at a crosshead rate of 20 mm / minute. Tensile properties of samples US-40 through 42 arc described in Tabic 19.

[0123] Table 18. Epoxy-Phosphate Ester Compositions Containing Secondary UnsaturationAttorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025| Total100.00 100.00 100.00

[0124] Table 19. Tensile Properties of Secondary Unsaturation Containing Compositions

[0125] As indicated in Table 19, the presence of a free radical source results in a 51.5% increase in tensile modulus for the peroxide containing sample US -41 and a 54.3% increase in tensile modulus for the azo containing sample US-42 compared to US-40, which does not contain a free radical source. This indicates that the addition of the free radical initiator provides some increased crosslinking of the secondary unsaturation contained in tire various epoxidized and phosphated natural oils in the composition.

[0126] As used herein, unless otherwise stated, the teachings envision that any member of a genus (list) may be excluded from the genus; and / or any member of a Markush grouping may be excluded from the grouping.

[0127] Unless otherwise stated, any numerical values recited herein include all values from the low er value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component, a property, or a value of a process variable such as. for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that intermediate range values such as (for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within the teachings of this specification. Likewise, individual intennediate values arc also within tire present teachings. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01. or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the low est value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. As can be seen, the teaching of amounts expressed as "parts by weight" herein also contemplates the same ranges expressed in terms of percent by weight. Thus, an expression in the of a range in terms of “at least ‘x’ parts by weight of the resulting composition" also contemplates a teaching of ranges of same recited amount of "x" in percent by w eight of the resulting composition."

[0128] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both ends of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30", inclusive of at least the specified endpoints.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025Unless otherwise stated, a teaching with the term “about" or “approximately" in combination with a numerical amount encompasses a teaching of the recited amount, as well as approximations of that recited amount. By way of example, a teaching of “about 100” encompasses a teaching of 100.

[0129] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for ail purposes. The term "consisting essentially of to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising" or "including" to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist of, or consist essentially of the elements, ingredients, components or steps.

[0130] Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of "a" or "one" to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps.

[0131] It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as well as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description. Tire scope of the invention should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with tire full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor should it be regarded that the inventors did not consider such subject matter to be part of the disclosed inventive subject matter.

Claims

Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 2025CLAIMSWe claim:

1. A two-component hybrid epoxy material comprising:- a first component including (i) at least one epoxy resin, and (ii) at least one oxidizing agent;- a second component including at least one acidic phosphorus material without olefinic unsaturation; wherein at least one olefinic unsaturated moiety is present in the first component or the second component or both; and wherein upon mixing tire first and second components a polymeric material comprising a reactive continuous phase is formed.

2. The two-component hybrid epoxy material of claim 1, wherein the at least one epoxy resin and at least one acidic phosphorous material are present in a total amount of at least about 50% of the reactive continuous phase by mass.

3. The two-component hybrid epoxy material of claim 1 or claim 2, wherein the at least one epoxy resin is an epoxy resin or blend of epoxy resins having an average molecular epoxide functionality of at least about 1.8.

4. The two-component hybrid epoxy material of any of the preceding claims, wherein the reactive continuous phase includes a cross linked network of the first and second components.

5. The two-component hybrid epoxy material of any of the preceding claims, wherein the at least one olefinic unsaturated moiety is selected from the group consisting of acrylates, methacrylates, allylics, vinylics and combinations thereof.

6. Tire two-component hybrid epoxy material of any of the preceding claims, wherein the at least one olefinic unsaturated moiety is monofunctional.

7. Tire two-component hybrid epoxy material of any of the preceding claims, wherein the at least one olefinic unsaturated moiety is difunctional.

8. The two-component hybrid epoxy material of any of the preceding claims, wherein the at least one olefinic unsaturated moiety is polyfunctional.

9. The two-component hybrid epoxy material of any of the preceding claims, wherein the oxidizing agent generates a free radical that polymerizes the at least one olefinic unsaturated moiety.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 202510. The two-component hybrid epoxy material of any of the preceding claims, wherein the oxidizing agent is selected from the group consisting of: peroxides, hydroperoxides, azo functional compounds, sulfonyl chloride containing compounds and photo sensitive radical initiators.

11. The two-component hybrid epoxy material of any of the preceding claims, wherein the oxidizing agent is thermally decomposed and generates a radical species.

12. The two-component hybrid epoxy material of any of the preceding claims, wherein the oxidizing agent is decomposed at room temperature wherein the two-component hybrid epoxy material further includes an accelerator and or a catalyst generating a radical species.

13. The two-component hybrid epoxy material of any of tire preceding claims, wherein the acidic phosphorous material is selected from the group consisting of: phosphoric acid, phosphonic acid and / or their esters, epoxy acid phosphate esters, alcohol acid phosphate esters, epoxy acid phosphonate esters, organo- phosphonates, alcohol acid phosphonate esters, and combinations thereof14. The two-component hybrid epoxy material of any of the preceding claims, wherein the acidic phosphorous material includes exactly one acidic phosphorous moiety or contains two or more acidic phosphorous moieties.

15. A two-component hybrid epoxy material comprising:- a first component including (i) at least one epoxy resin, and (ii) at least one oxidizing agent;- a second component including at least one acidic phosphorus material with olefinic unsaturation; wherein upon mixing of the first and second components a polymeric material is formed having a reactive continuous phase, and wherein the at least one epoxy resin and the at least one acidic phosphorous material is present in a total amount of at least about 50% of the reactive continuous phase by mass.

16. The two-component hybrid epoxy material of claim 15, wherein upon mixing the first and second components a continuous epoxy-phosphate ester network is formed.

17. The two-component hybrid epoxy material of claim 15 or claim 16, wherein the at least one epoxy resin is an epoxy resin or blend of epoxy resins having an average molecular epoxide functionality of at least about 1.8.

18. The two-component hybrid epoxy material of any of claims 15 through 17, wherein the reactive continuous phase includes a cross linked network of the first and second components.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 202519. The two-component hybrid epoxy material of any of claims 15 through 18, wherein the oxidizing agent generates a free radical polymerizing the at least one olefinic unsaturated moiety.

20. The two-component hybrid epoxy material of any of claims 15 through 19, wherein the oxidizing agent is selected from the group consisting of: peroxides, hydroperoxides, azo functional compounds, sulfonyl chloride containing compounds and photo sensitive radical initiators.

21. The two-component hybrid epoxy material of any of claims 15 through 20, wherein the oxidizing agent is thermally decomposed and generates a radical species.

22. The two-component hybrid epoxy material of any of claims 15 through 21, wherein the oxidizing agent is decomposed at room temperature and wherein the two-component hybrid epoxy material further includes an accelerator and or a catalyst generating a radical species.

23. The two-component hybrid epoxy material of any of claims 15 through 22, wherein the acidic phosphorous material is selected from the group consisting of: phosphoric acid, phosphonic acid and / or their esters thereof, epoxy acid phosphate esters, alcohol acid phosphate esters, epoxy acid phospho- nate esters, organo- phosphonates, alcohol acid phosphonate esters, and combinations thereof.

24. Tire two-component hybrid epoxy material of any of claims 15 through 23, wherein tire acidic phosphorous material includes one acidic phosphorous moiety or contains two or more acidic phosphorous moieties.

25. A two-component hybrid epoxy material comprising:- a first component including (i) at least one epoxy resin, and (ii) at least one oxidizing agent;- a second component including (i) at least one acidic phosphorus material without olefinic unsaturation, and (ii) at least one acidic phosphorus material with olefinic unsaturation; wherein upon mixing of the first and second components a polymeric material is formed having a reactive continuous phase, and wherein the at least one epoxy resin and at least one acidic phosphorous material is present in a total amount of at least about 50% of the reactive continuous phase by mass.

26. The two-component hybrid epoxy material of claim 25, wherein upon mixing of the first and second components a continuous epoxy-phosphate ester network is formed.

27. The two-component hybrid epoxy material of claim 25 or claim 26, wherein the at least one epoxy resin is an epoxy resin or blend of epoxy resins having an average molecular epoxide functionality of at least about 1.8.Attorney Docket No. 1001.924USWOFiled Via USPTO.GOV on August 29, 202528. The two-component hybrid epoxy material of any of claims 25 through 27, wherein tire reactive continuous phase includes a cross linked network of tire first and second components.

29. The two-component hybrid epoxy material of any of claims 25 through 28, wherein the oxidizing agent generates a free radical polymerizing the at least one olefinic unsaturated moiety.

30. The two-component hybrid epoxy material of any of claims 25 through 29, wherein the oxidizing agent is selected from the group consisting of: peroxides, hydroperoxides, azo functional compounds, sulfonyl chloride containing compounds and photo sensitive radical initiators.

31. Tire two-component hybrid epoxy material of any of claims 25 through 30, wherein the oxidizing agent is thermally decomposed and generates a radical species.

32. The two-component hybrid epoxy material of any of claims 25 through 31, wherein the oxidizing agent is decomposed at room temperature and wherein the two-component hybrid epoxy material further includes an accelerator and or a catalyst generating a radical species.

33. The two-component hybrid epoxy material of any of claims 25 through 32, wherein the acidic phosphorous material is selected from the group consisting of: phosphoric acid, phosphonic acid and / or their esters thereof, epoxy acid phosphate esters, alcohol acid phosphate esters, epoxy acid phospho- nate esters, organo- phosphonates, alcohol acid phosphonate esters, and combinations thereof.

34. The two-component hybrid epoxy material of any of claims 25 through 33, wherein the acidic phosphorous material includes one acidic phosphorous moiety or contains two or more acidic phosphorous moieties.

35. Use of the two-component hybrid epoxy material of any of the preceding claims as a structural adhesive or as a component of a structural adhesive.

36. Use of the two-component hybrid epoxy material of any of the preceding claims as a structural foam or as a component of a structural foam.

37. Use of the two-component hybrid epoxy material of any of the preceding claims as a room temperature cured adhesive.

38. Use of tire two-component hybrid epoxy material of any of the preceding claims as an adhesive on a vehicle component or within a vehicle cavity.

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