Two-component acidic phosphorous cured epoxy composition

Abstract

The present teachings provide for a polymerizable, two-component material with improved physical and / or adhesive properties, wherein one component is an epoxy resin or blend of epoxy resins where the average epoxide functionality is at least about 2 per molecule, and the other component is an acidic phosphorous ester of a di or greater functional epoxide, hydroxyl and / or hydroxide containing molecule or a blend of said acidic phosphorous ester with phosphoric acid, phosphonic acid, and / or their acidic esters.

Description

Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025TWO-COMPONENT ACIDIC PHOSPHOROUS CURED EPOXY COMPOSITIONCLAIM OF PRIORITY

[0001] This application claims the benefit of the priority date of United States Provisional Application Serial No. 63 / 684,143, filed on August 16, 2024. The contents of that application are incorporated by reference herein in their entirety and for all purposes.FIELD

[0002] The present teachings relate generally to a polymerizable, two-component material with improved physical and / or adhesive properties.BACKGROUND

[0003] It has long been known that phosphoric acid can be used to rapidly cure epoxy resins. However, due to the exceedingly fast reaction rate between the tri-functional acids and di or greater functional epoxy resins, little commercial success had been found with this polymerization technique. As described in United States Patent No. 10,550,220 (which is incorporated by reference herein in its entirety and for all purposes) 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 the reactivity of the material with epoxy resins to the point at which they have similar reaction speeds to commonly used rapid epoxy curatives in market, such as accelerated mercaptans, while at the same time increasing the equivalent weight per reactive hydrogen.

[0004] However, United States Patent No. 10,550,220 focuses on the esterification of monoepoxide molecules to be used as the acidic phosphorous containing epoxy curatives. This results in linear chain growth of the resulting cured polymer. Crosslinking of the polymer is controlled primarily by the functionality of the liquid epoxy blend, and the resulting polymeric structures are limited by the structure of the epoxy resin(s) used.

[0005] Using an acidic phosphorous ester of a di or greater functional epoxide, hence forth referred to as a polyacid phosphate (PAP), as the sole curative or in the blend of acidic phosphorous containing curatives can provide a multitude of benefits such asAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 improved adhesive properties, improved physical properties, gel time control, exotherm reduction, and more equalized volumetric mix ratio.

[0006] Acidic phosphorous materials are ideal curatives for epoxies that are bonding to one or more substrates. Acidic phosphorous materials react directly with a variety of substrates including, but not limited to, siliceous, cementitious, metal, and ceramic materials, forming covalent or ionic bonds with the substrates. As such, the acidic phosphorous component performs both the role of primary curative and adhesion promoter. Due to the high degree of adhesion generated on a variety of substrates, acidic phosphorous cured epoxy materials are ideal for adhesives, capable of generating high overlap shear strength and high peel strength bonds on unabraded metals.

[0007] Notwithstanding the above teachings, there has remained a need for polymerizable epoxy-based materials that are cured with acidic phosphorous materials while having improved adhesion and physical properties. The present teachings provide one or more of the above mentioned benefits.SUMMARY

[0008] The teachings herein are directed to a two-part composition comprising Part A including at least one epoxy resin having an average molecular epoxide functionality of at least 2, and Part B including at least one acidic phosphorous containing molecule, the acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties.

[0009] Part A may comprise a blend of epoxy resins.

[0010] Part A may include at least one resin selected from the group consisting of: cyclic epoxy resins, linear epoxy resins, or an epoxy resin containing a blend of cyclic and linear components.

[0011] Part A may include at least one resin selected from the group consisting of: Bisphenol A diglycidyl ether, 1 ,6 hexane diol diglycidyl ether, an epoxy adduct of dimer fatty acid, or any combination thereof.

[0012] A reactive epoxide group of the at least one epoxy resin may be terminal, secondary, or pendant.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0013] The at least one acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties may be present in an amount of from 20 to 100 weight percent of Part B.

[0014] The Part B may have a backbone that is linear, branched, cyclic, or a blend of linear and cyclic components.

[0015] The Part B may have a backbone that is an addition reaction product including an acidic phosphorous material with a di or greater functional alcohol material, or an acidic phosphorous material with a di or greater functional epoxide material.

[0016] The Part B may have a backbone that is a polymer or copolymer of 2-HEMA Phosphate Ester wherein the wherein the molecular weight of the ester is increased through a reaction at the carbon-carbon double bond of the HEMA moiety.

[0017] The Part B may include acidic phosphorous materials such that only one phosphorous atom contains acidic hydrogens.

[0018] The Part B may include a dehydrated acidic phosphorous component.

[0019] A ratio of Part A to Part B may be less than 4: 1 by volume.

[0020] An acid equivalent weight (AEW) of the least one acidic phosphorous containing molecule having at least two acidic phosphorous moieties of Part B may be greater than 40 g / eq.

[0021] Part A may include a metal carbonate.

[0022] Part A may include wollastonite, talc, ground rubber, fumed or precipitated silicas, fly ash, clays, resinous dust, or any combination thereof.

[0023] Part A may include a phenoxy material.

[0024] The teachings herein are further directed to a two-part composition comprising Part A including at least one epoxy resin having an average molecular epoxide functionality of at least 2 and Part B including at least one acidic phosphorous containing molecule, the acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties. Part B has a backbone that is a polymer or copolymer of 2-HEMA Phosphate Ester wherein the wherein the molecular weight of the ester is increased through a reaction at the carbon-carbon double bond of the HEMA moiety.

[0025] The teachings herein are also directed to a two-part composition comprising Part A including at least one epoxy resin having an average molecular epoxideAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 functionality of at least 2 and Part B including at least one acidic phosphorous containing molecule, the acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties. The at least one acidic phosphorous containing molecule is selected from butyl acid phosphate, 2-HEMA phosphate, castor oil phosphate, bisphenol F liquid epoxy polyacid phosphate, and combinations thereof, the at least one acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties is present in an amount of from 20 to 100 weight percent of Part B, and a ratio of Part A to Part B is less than 4:1 by volume.

[0026] The composition may be adapted to foam upon combining the Part A and Part B.

[0027] Part A may include a metal carbonate selected from zinc carbonate, calcium carbonate, magnesium carbonate, and combinations thereof.

[0028]

[0029] Part A may include a phenoxy component dissolved in a bisphenol A liquid epoxy.

[0030] Part B may include phosphoric acid, which may be a polyphosphoric acid.

[0031] Part B may include an epoxidized castor oil.

[0032] The ratio of Part A to Part B is about 2: 1 .

[0033] The teachings herein are directed to compositions which solve the need for acidic phosphorous cured epoxy compositions having improved physical properties and simplified mix ratios where the ratio by volume of Part A and Part B is closer to 2: 1 .DETAILED DESCRIPTION

[0034] The 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 the teachings. The scope of the teachings should, therefore, be determined not with reference to the above description, but shouldAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 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. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

[0035] A composition for a two-component, acidic phosphorous cured epoxy composition with improved properties is disclosed herein. Part A of the composition is an epoxy resin or blend of epoxy resins with an average molecular epoxide functionality of at least about 2. Part B of the composition is an acidic phosphorous containing molecule or blend of acidic phosphorous containing molecules, wherein at least one of the acidic phosphorous containing molecules contains at least two acidic phosphorous moieties in the acidic curative component. Such a composition is demonstrated to improve properties over compositions containing phosphoric acid, phosphonic acid, their mono-alcohol and mono-epoxide esters, and blends thereof.

[0036] Part A of the composition is an epoxy resin or blend of epoxy resins having an average molecular epoxide functionality of at least about two. Said blend of resins may be composed of cyclic epoxy resins, such as Bisphenol A diglycidyl ether, linear epoxy resins, such as 1 ,6 hexane diol 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, although other epoxide functionalities can be contemplated and terminal position is not necessary for effective reaction.

[0037] Part B of the composition is an acidic phosphorous containing molecule or blend of acidic phosphorous containing molecules, wherein at least one of the acidic phosphorous containing molecules contains at least two acidic phosphorous moieties (PAP). The PAP material backbone may be linear, branched, cyclic or a blend of linear and cyclic components. Preferably, the PAP backbone is linear or a blend of linear and cyclic components. The PAP may be an addition reaction product with, but not limited to, an acidic phosphorous material with a di or greater functional alcohol material, or an acidic phosphorous material with a di or greater functional epoxide material. The PAP may beAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 formed either through controlled synthetic reactions, or through an -in-situ reaction with one or more acidic phosphorous materials. The PAP may be a polymer or copolymer of 2-HEMA phosphate ester, wherein molecular weight of the ester is increased through a reaction at the carbon-carbon double bond of the HEMA moiety.

[0038] Part B of the composition may also, optionally, include acidic phosphorous materials wherein only one phosphorous atom contains acidic hydrogens. Such materials include, but are not limited to phosphoric acid, its monoesters and diesters thereof, as well as phosphonic acid and its monoesters. Part B of the composition may also, optionally, include molecules with two or more acidic phosphorous atoms wherein the average acid equivalent weight (AEW) is less than 250 g / eq. Part B of the composition may also, optionally, include dehydrated acidic phosphorous components, including but not limited to, polyphosphoric acid and phosphorous pentoxide.

[0039] A composition for a two-component, acidic phosphorous cured epoxy composition with improved mix ratio and physical properties is disclosed herein. A first part A of the composition is an epoxy resin or blend of epoxy resins with an average molecular epoxide functionality of at least about 2. The part B of the composition is an acidic phosphorous containing molecule or blend of acidic phosphorous containing molecules, wherein at least one of the acidic phosphorous containing molecules contains at least two acidic phosphorous moieties, denoted as the PAP material, preferably in the amount of 20 - 100 weight percent of the acidic phosphorous containing molecules. Such a composition has been demonstrated to improve properties.

[0040] Part A of the composition is an epoxy resin or blend of epoxy resins having an average molecular epoxide functionality of at least about two. Said blend of resins may be composed of cyclic epoxy resins, such as bisphenol A diglycidyl ether, linear epoxy resins, such as 1 ,6 hexane diol 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, as is in bisphenol A diglycidyl ether, secondary in nature, such as epoxidized soybean oil, or pendant as in epoxidized castor oil or other oxirane functional molecules.

[0041] Part B of the composition is an acidic phosphorous containing molecule or blend of acidic phosphorous containing molecules, wherein at least one of the acidicAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 phosphorous containing molecules is the PAP material. The PAP material backbone may be linear, branched, cyclic, or a blend of linear and cyclic components. Preferably, the PAP backbone is linear or a blend of linear and cyclic components. The PAP may be formed by an addition reaction with, including but not limited to, an acidic phosphorous material containing at least two acidic hydrogens with a di or greater functional alcohol material, or an acidic phosphorous material containing at least two acidic hydrogens with a di or greater functional epoxide material. The PAP may be formed either through controlled synthetic reactions, or through an -in-situ reaction with a, or a blend of, lower molecular weight acidic phosphorous material(s) or a blend of lower molecular weight acidic phosphorous materials. The PAP may be a copolymer of 2-HEMA phosphate ester, or similar polymerized olefinic acidic phosphorous monomer, wherein the molecular weight of the ester is increased through a reaction at the carbon-carbon double bond of the HEMA moiety.

[0042] PAP materials, particularly those formed with phosphoric or polyphosphoric acid, may form a ladder-like structure with di-functional epoxy resins. Depending on the structure of the PAP, improvement in properties may be obtained in comparison to the linear growth polymers formed with acidic phosphorous containing esters of monofunctional epoxies and alcohols.

[0043] As described in patent number US 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 the reactivity of the material with epoxy resins to the point at which they have similar reaction speeds to commonly used rapid epoxy curatives in market, such as accelerated mercaptans. However, even with the reduction of acidic hydrogens and increased molecular weight of the esterified phosphoric or phosphonic acids compared to unesterified acids, the most common volumetric mix ratio for the aforementioned acid cured epoxy systems remains at a disparate 4:1 epoxy to acid ratio.

[0044] There are many reasons for this. Known to those skilled in the art, many other addition cured reactions, including but not limited to isocyanate-polyol reactions, isocyanate-amine reactions, and epoxy-amine reactions, often have an equivalent weightAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 ratio of reactive functional groups of no greater than 1.1 :1 to generate maximum properties. However, in acidic phosphorous cured epoxy materials, there are two competing polymerization reactions in cationic homopolymerization of the epoxy functional material, as well as esterification of the acidic phosphorous group with the epoxy functional material. As such, ideal properties may be generated in an acidic phosphorous cured epoxy system with between 1 :1 to 2.5:1 epoxy:acid equivalents depending on the formula, with ideal properties often being generated around 1.5:1 to 2: 1 epoxy to acid equivalents. As such, substantially less acid is generally necessary to cure the epoxy material than available epoxide groups. Another reason for the non-ideal mix ratio is a matter of equivalent weight of available epoxy resins vs that of the acidic esters. DER331 , a Bisphenol A epoxy resin, has an average epoxy equivalent weight (EEW) of 187 g / eq, and epoxy functional materials for physical property improvement generally increase in EEW from there. Conversely, 2-hydroxy ethyl methacrylate mono phosphate ester has an acid equivalent weight (AEW) of approximately 105 g / eq, substantially lower than the EEW of the most common epoxy resin type. Lastly, acidic phosphorous materials are generally more dense than the purely organic epoxy resins. All of the aforementioned factors lead to a 4:1 volumetric mix ratio being commonly used.

[0045] The use of the PAP material in an epoxy curative composition addresses the mix ratio disparity in two ways. First, by having an AEW of greater than, or substantially greater than the EEW of commonly used epoxy resins, such as bisphenol A diglycidyl ether, volumetric mix ratios approaching 1 :1 or acidic curative dominant systems are possible. Additionally, as the AEW of the PAP increases, the density of the material approaches that of its native alcohol or epoxy, which can also help to further extend the acidic curative without the need for non-reactive extenders.

[0046] The present composition may include dyes or pigments. These materials may be organic or inorganic in nature and may be present for purely aesthetic reasons or additional reasons. Additional uses beyond the aesthetic include, but are not limited to, UV blocking, reinforcing, 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. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0047] Filler type materials can be added to the resin component, the acidic component, or both. Said materials should have a particle size of no more than about 1 mm to maintain material flowability. Such materials may be organic or inorganic in nature. They may have a variety of shapes including spherical, cubic, platelet, needle, or fiberlike. They may provide, including but not limited to, mix ratio control, reinforcing, rheological control, density control, dimensional stability, and / or impact resistance to the polymer matrix. Examples of such materials include wollastonite, talc, ground rubber, fumed or precipitated silicas, fly ash, clays, resinous dust, and a variety of other minerals and micronized waste products.

[0048] In the presence of acidic additive or curative material, some fillers provide additional secondary effects. Metal carbonate materials release carbon dioxide via a decomposition reaction upon contact with an acid. The generated gas from this reaction can be trapped during the polymerization process to create a foamed product. This may be useful for improving adhesion, as well as counteracting the effect of shrinkage during the polymerization process. Potential metal carbonates for use in the materials described herein include zinc carbonate, calcium carbonate, magnesium carbonate, and combinations thereof.

[0049] Impact modifiers may also be added to the resin component, acidic component, or both. These materials are added 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 at least about -40°C. These materials may be liquid or solid particles. Said materials may or may not react into the binding resin matrix. Additionally, these materials 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 or ground tire rubber.

[0050] 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 materials work by having strong light absorption peaks in the ultraviolet range of the electromagnetic radiation spectrum. This reduces the probability of light in the ultraviolet spectrum being absorbed by the resin matrix, causing unwanted degradation. Unlike UVA materials, HALS do not absorb aAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 substantial amount of UV light. Such materials react with photoradicals, converting them to less damaging peroxy species. Examples of UVA materials include but are not limited to Poly(oxy-1 ,2-ethanediyl), ,alpha.-[3-[3-(2H-benzotriazol-2-yl)-5- (1 ,1 -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(1 , 2, 2,6,6- pentamethyl-4-piperidyl)sebacate, and methyl 1 ,2,2,6,6-pentamethyl-4-piperidyl sebacate.

[0051] In certain instances, surfactant type materials may be added to the epoxy component, acidic component or both with varying functions including substrate and filler wetting, viscosity reduction, air release, and defoaming. Wetting is a process in which a surfactant displaces 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.

[0052] In certain embodiments, plasticizing materials may be added to the epoxy component, acidic component or both. These materials are typically of low molecular weight and do 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 the reactive components when dispensed from a volumetric ratio, dualcomponent cartridge.

[0053] In certain embodiments, dehydrating the epoxy component, acidic component or both may be advantageous. Dehydration may occur through both chemical reaction and by entrapment. Chemical dehydration includes an additive chemical that may react with the water entrained in the continuous phase of either the 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 oxides. This list of materials is to be considered to be conceptually representative and is not a fully inclusive list of materials.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0054] Alternatively, physical entrapment of the water may also be used to remove water entrained in either the resinous component, acidic 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 are not limited to, anhydrous copper sulfate and calcium sulfate hemihydrate. An additional method of water entrapment is through the use of incorporating highly hydrophilic particles into the continuous phase of the 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, silica gel, and sodium polyacrylate.

[0055] In certain embodiments, use of solid, high molecular weight resins may be beneficial for enhancing the physical properties of the cured resin matrix. 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 materials include, but are not limited to, (meth)acrylate polymers and copolymers, phenoxy resins, urethane resins, polyvinyl alcohols, polyvinyl butyrals, ethylene vinyl acetates, and cellulosic resins.

[0056] Example 1

[0057] Example 1 illustrates the use of a linear poly-epoxide functional molecule, epoxidized castor oil, for generating the PAP material. The specifics of the composition are detailed in formulation 1 , in Table 1 . Formulation 1 is compared to a composition in which the epoxidized castor oil does not undergo phosphorylation and is added to the epoxy component in Formulation 2.

[0058] Part A of each formulation was mixed under vacuum via a SpeedMixer® until all constituents were mixed. Part B of Formulation 1 was produced with the following process: 85% phosphoric acid and butyl acid phosphate from IsleChem were added to a SpeedMixer® cup and mixed by hand until homogenous. The epoxidized castor oil was then added to the mixing cup and immediately mixed by a SpeedMixer® to mix all components. This mixture was allowed to sit for at least 30 minutes prior to adding the 2- HEMA phosphate and mixing until homogenous. All part B constituents of Formulation 2 were added to a SpeedMixer® cup and mixed until homogenous.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0059] For all testing, Formulation 1 was mixed 2:1 by mass, and Formulation 2 was mixed 13:2 by mass. Mixing of the two components was done by hand in a suitable mixing container with a tongue depressor. Overlap shear testing was performed on 2 mm thick 6061 aluminum, with a 12.7 mm overlap and 0.25 mm bond line, at a crosshead speed of 10 mm / minute. T-peel testing was performed on 0.9 mm thick 6022 aluminum, with a 0.25 mm bond line, at a crosshead speed of 100 mm / minute.

[0060] Table 1 - Compositions with and without Epoxy-Based Linear Polyacid Phosphate Curatives

[0061] Table 2 - Adhesive and Curing Properties of Table 1 CompositionsAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0062] While the two compositions use the same ingredient set, molecular architecture from the use of the PAP in Formulation 1 resulted in an extended gel time, which may be beneficial in many assembly applications. Additionally, Formulation 1 had a 44% improvement in T-Peel performance vs Formulation 2, while only experiencing a 14% reduction in overlap shear strength. Additionally, Formulation 1 has much less disparate mix ratio than Formulation 2, 2:1 vs 13:2 respectively by mass, which aids in quality of mixing and user convenience.

[0063] Example 2

[0064] Example 2 illustrates the use of a dimer diol, under the tradename Pripol 2033-LQ, for generation of the PAP material. This composition is compared to a similar composition wherein the dimer diol is not phosphorylated prior to mixing of the A and B components of the formulation, as well as a composition that uses a glycidyl ester of dimer fatty acid, under the tradename Kukdo YD-171 , in the epoxy component in place of the dimer diol.

[0065] Part A of each formulation described in Table 3 was mixed under vacuum via a Speed Mixer® until homogenous. Part B of Formulation 3 was produced with the following process: Polyphosphoric acid and butyl acid phosphate were added to a speed mixing cup and mixed via a SpeedMixer® until homogenous. The rest of the constituents were added and mixed under vacuum via a SpeedMixer® until all constituents were mixed. This composition was allowed to sit overnight prior to testing. All components of part B of Formulations 4 and 5 were added to a SpeedMixer® cup and mixed under vacuum via a SpeedMixer® until homogenous.

[0066] For all testing, Formulation 3 was mixed at a mix ratio of 2:1 by mass, parts A:B respectively. Formulations 4 and 5 were mixed at a ratio 25.4:4.6 by mass. All samples were mixed by hand with a tongue depressor, and all samples were allowed to cure for 24 h at ambient temperature prior to testing. Tensile samples were prepared in accordance with EN ISO 527-2 1 B, and tensile testing was performed at a crosshead speed of 50 mm / minute.

[0067] Table 3 - Compositions with and without Dimer Diol Derived PAPAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0068] Table 4 - Tensile and Curing Properties of Table 3 Composition

[0069] When comparing Formulations 3 and 4, which use the same ingredient set, but vary molecular architecture, it can be seen that the phosphorylated dimer diol of Formulation 3 provides an extended gel time. The tensile modulus of Formulation 3 is slightly lower than that of Formulation 4 (9.3 MPa vs 13 MPa), however Formulation 3 has a 48% higher tensile strength (3.7 MPa vs 2.5 MPa), as well as a 53% increase in tensile elongation (84.1% vs 54.9%.). When comparing Formulation 3 to Formulation 5, the differences in the resulting polymer are even more stark. Formulation 3 has aAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 significantly lower tensile modulus than Formulation 5 (9.3 MPa vs 252.1 MPa), but attains a 76% higher tensile strength and 7008% higher tensile elongation (84.1 % vs 1.2%). This again demonstrates that forming a PAP in part B can yield a very different balance of useful property in formulations.

[0070] Example 3

[0071] Example 3 demonstrates the use of bisphenol F epoxy resin to form an acidic di-phosphate ester for a 1 :1 mix ratio composition. Said PAP was formed by mixing 1 part liquid bisphenol F epoxy resin with 2 parts of a mono phosphate ester formed from the reaction product of 85% phosphoric acid and 2-ethylhexyl glycidyl ether. The PAP composition then sat overnight under ambient conditions to react. The resulting PAP composition was then mixed 92 parts to 8 parts 85% phosphoric acid until the composition was homogeneous.

[0072] The above composition curative was mixed 1 :1 by mass in an appropriate container with a tongue depressor. Overlap shear testing was performed on 1 .5 mm thick, solvent cleaned cold rolled steel, with a 12.7 mm overlap and 0.25 mm bond line, at a crosshead speed of 10 mm / minute. Overlap shear specimens cured for 24 hours at ambient temperature prior to testing.

[0073] Table 5 - 1 :1 Mix Ratio Composition with Cyclic Epoxide PAP

[0074] Table 6 - Properties of Formulation 6

[0075] The results outlined in Table 6 show that a rapidly-curing, 1 :1 mix ratio adhesive is possible when utilizing a PAP.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0076] Example 4

[0077] Example 4 demonstrates a foaming composition utilizing a PAP derived from castor oil. 80 parts number 1 castor oil was mixed with 20 parts 115% polyphosphoric acid 80°C for 4 hours. The resulting castor oil phosphate was used in Formulation 7 described in Table 7 below.

[0078] Parts A and B of Formulation 7 were mixed under vacuum via a SpeedMixer® until all constituents were mixed. Parts A and B were mixed 4:1 by mass, respectively, in an appropriate container via a tongue depressor.

[0079] Table 7 - Foaming Composition Utilizing a PAP

[0080] When mixed, Formulation 7 underwent 40% volumetric expansion and formed a thermoset network with an E’ T(g) of 45°C. This demonstrates that PAP material may be utilized in foaming compositions.

[0081] Example 5

[0082] Example 5 demonstrates the use of a PAP wherein the phosphate ester is formed from a hydroxyl containing copolymer of styrene and allyl alcohol.

[0083] Blending Part A of Formulation 8 is described in Example 1. Part B of Formulation 8 is compounded by the following methodology: 67 parts of a phosphorylatedAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 styrene allyl alcohol copolymer dissolved in isobutanol under the trade name Lubrizol 2062H was mixed with 33 parts of 115% polyphosphoric acid under nitrogen, with a stir bar set to 150 rpm, and a heater set point of 50°C for 19 minutes. The heater was then set to 65°C and was allowed to mix for 1 hour and 46 minutes and subsequently cool to room temperature. 60 parts of the resulting product was then mixed under vacuum via a SpeedMixer® with 30 parts IsleChem Butyl Acid Phosphate and 10 parts 85% phosphoric acid.

[0084] Table 8 - Formulation Utilizing a PAP Derived from a Hydroxyl Containing Polymer

[0085] Formulation 8 was used to fill a 2:1 volumetric cartridge. Said composition was dispensed through a 10-24 helical static mixer onto 1.5 mm thick, solvent cleaned cold rolled steel to make overlap shear specimens with a 12.7 mm overlap and 0.25 mm bond line. Said samples were allowed to cure for 24 hours and then tested in shear with a 10 mm / min crosshead speed.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0086] The resulting adhesive composition had an overlap shear strength of 11 .9 MPa, demonstrating that a polymer derived PAP may be utilized as an appropriate epoxy curative.

[0087] 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.

[0088] Unless otherwise stated, any numerical values recited herein include all values from the lower 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 intermediate values are also within the 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 lowest 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 weight of the resulting composition."

[0089] 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. Unless 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.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025

[0090] 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.

[0091] 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.

[0092] 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. The 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 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. 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. 1001.922WOFiled Via USPTO.GOV on August 18, 2025CLAIMSWe claim:1 . A two-part composition comprising:Part A including at least one epoxy resin having an average molecular epoxide functionality of at least 2;Part B including at least one acidic phosphorous containing molecule, the acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties.

2. The two-part composition of claim 1 , wherein Part A comprises a blend of epoxy resins.

3. The two-part composition of claim 1 or claim 2, wherein Part A includes at least one resin selected from the group consisting of: cyclic epoxy resins, linear epoxy resins, or an epoxy resin containing a blend of cyclic and linear components.

4. The two-part composition of any of the preceding claims, wherein Part A includes at least one resin selected from the group consisting of: Bisphenol A diglycidyl ether, 1 ,6 hexane diol diglycidyl ether, an epoxy adduct of dimer fatty acid, or any combination thereof.

5. The two-part composition of any of the preceding claims, wherein a reactive epoxide group of the at least one epoxy resin is terminal.

6. The two-part composition of any of the preceding claims, wherein a reactive epoxide group of the at least one epoxy resin is secondary.

7. The two-part composition of any of the preceding claims, wherein a reactive epoxide group of the at least one epoxy resin is pendant.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 20258. The two-part composition of any of the preceding claims, wherein the at least one acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties is present in an amount of from 20 to 100 weight percent of Part B.

9. The two-part composition of any of the preceding claims, wherein the Part B has a backbone that is linear, branched, cyclic, or a blend of linear and cyclic components.

10. The two-part composition of any of the preceding claims, wherein the Part B has a backbone that is an addition reaction product including an acidic phosphorous material with a di or greater functional alcohol material, or an acidic phosphorous material with a di or greater functional epoxide material.

11. The two-part composition of any of the preceding claims, wherein the Part B has a backbone that is a polymer or copolymer of 2-HEMA Phosphate Ester wherein the wherein the molecular weight of the ester is increased through a reaction at the carboncarbon double bond of the HEMA moiety.

12. The two-part composition of any of the preceding claims, wherein Part B includes acidic phosphorous materials such that only one phosphorous atom contains acidic hydrogens.

13. The two-part composition of any of the preceding claims wherein Part B includes a dehydrated acidic phosphorous component.

14. The two-part composition of any of the preceding claims, wherein a ratio of Part A to Part B is less than 4:1 by volume.

15. The two-part composition of any of the preceding claims, wherein an acid equivalent weight (AEW) of the least one acidic phosphorous containing molecule having at least two acidic phosphorous moieties of Part B is greater than 40 g / eq.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 202516. The two-part composition of any of the preceding claims, wherein Part A includes a metal carbonate.

17. The two-part composition of any of the preceding claims, wherein Part A includes wollastonite, talc, ground rubber, fumed or precipitated silicas, fly ash, clays, resinous dust, or any combination thereof.

18. The two-part composition of any of the preceding claims, wherein Part A includes a phenoxy material.

19. A two-part composition comprising:Part A including at least one epoxy resin having an average molecular epoxide functionality of at least 2;Part B including at least one acidic phosphorous containing molecule, the acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties; wherein Part B has a backbone that is a polymer or copolymer of 2-HEMA Phosphate Ester wherein the wherein the molecular weight of the ester is increased through a reaction at the carbon-carbon double bond of the HEMA moiety.

20. A two-part composition comprising:Part A including at least one epoxy resin having an average molecular epoxide functionality of at least 2;Part B including at least one acidic phosphorous containing molecule, the acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties; wherein the at least one acidic phosphorous containing molecule is selected from butyl acid phosphate, 2-HEMA phosphate, castor oil phosphate, bisphenol F liquid epoxy polyacid phosphate, and combinations thereof; andAttorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 2025 wherein the at least one acidic phosphorous containing molecule having at least two separate acidic phosphorous moieties is present in an amount of from 20 to 100 weight percent of Part B; and wherein a ratio of Part A to Part B is less than 4:1 by volume.21 . The two-part composition of any of the preceding claims, wherein the composition is adapted to foam upon combining the Part A and Part B.

22. The two-part composition of claim 20 or 21 , wherein Part A comprises a blend of epoxy resins.

23. The two-part composition of any of claims 20 through 22, wherein Part A includes at least one resin selected from the group consisting of: cyclic epoxy resins, linear epoxy resins, or an epoxy resin containing a blend of cyclic and linear components.

24. The two-part composition of any of claims 20 through 23, wherein Part A includes at least one resin selected from the group consisting of: Bisphenol A diglycidyl ether, 1 ,6 hexane diol diglycidyl ether, an epoxy adduct of dimer fatty acid, or any combination thereof.

25. The two-part composition of any of claims 20 through 24, wherein a reactive epoxide group of the at least one epoxy resin is terminal.

26. The two-part composition of any of claims 20 through 25, wherein a reactive epoxide group of the at least one epoxy resin is secondary.

27. The two-part composition of any of claims 20 through 26, wherein a reactive epoxide group of the at least one epoxy resin is pendant.Attorney Docket No. 1001.922WOFiled Via USPTO.GOV on August 18, 202528. The two-part composition of any of claims 20 through 27, wherein Part A includes a metal carbonate.

29. The two-part composition of any of claims 20 through 28, wherein Part A includes wollastonite, talc, ground rubber, fumed or precipitated silicas, fly ash, clays, resinous dust, or any combination thereof.

30. The two-part composition of any of claims 20 through 29, wherein Part A includes a phenoxy material.31 . The two-part composition of any of the preceding claims, wherein Part A includes a metal carbonate selected from zinc carbonate, calcium carbonate, magnesium carbonate, and combinations thereof.

32. The two-part composition of any of the preceding claims, wherein Part A includes a phenoxy component dissolved in a bisphenol A liquid epoxy.

33. The two-part composition of any of the preceding claims, wherein Part B includes phosphoric acid, which may be a polyphosphoric acid.

34. The two-part composition of any of the preceding claims, wherein Part B includes an epoxidized castor oil.

35. The two-part composition of any of the preceding claims, wherein the ratio of Part A to Part B is about 2:1 .