EP4702069A1 - Ambient temperature rapid cure system of oxirane-containing compounds - Google Patents

Abstract

An adhesive comprising an oxirane-containing compound and an acidic phosphorous curative. The adhesive gels, at a temperature of about 0 °C to 50 °C and upon mixing the aliphatic disubstituted oxirane and the acidic phosphorous curative, in about 10 minutes or less.

Description

AMBIENT TEMPERATURE RAPID CURE SYSTEM OF OXIRANE-CONTAINING COMPOUNDS

CLAIM OF PRIORITY

[001] This application claims the benefit of the priority of U.S. Provisional Application No. 63/461 ,732, filed on April 25, 2023, which is incorporated by reference herein in its entirety and for all purposes.

FIELD

[002] The present teachings generally relate to an ambient temperature, rapid cure system and two-part compositions formulated with the same. The rapid cure system utilizes a curing reaction of oxirane-containing compounds with acidic phosphorous curatives. The present teachings may be particularly suited to oxirane-containing compounds that are non-epichlorohydrin-derived and typically react too slowly with traditional epoxy curatives to render useful products.

BACKGROUND

[003] Glycidyl ethers (Structure I, below) and glycidyl amines (Structure II, below) can react and crosslink at ambient temperature (i.e., about 20 °C to 25 °C) with many known curatives to form addition products. They can also be induced to homopolymerize at ambient temperature by several known classes of catalysts.

[004] Glycidyl ethers of aromatic phenols are particularly well suited for crosslinking reactions to provide for three-dimensional thermoset networks. For example, the diglycidyl ether of bisphenol A (“DGEBA”) (Structure I where R¹ is 4,4'-substituted 2,2-diphenylpropane) is known to react, in an addition reaction, at ambient temperature with curatives such as aromatic or aliphatic amines, mercaptans or thiols, acid anhydrides, and carboxylic acids with the reaction rates differing among the types of reactants.

[005] DGEBA can be induced to homopolymerize at ambient temperature by catalysts such as tertiary amines, substituted imidazoles, and amine complexes of Lewis acids such as BF₃.

[006] Aromatic glycidyl amines (e.g., Structure II where R³ is an aromatic group such as diphenyl methane) react similarly to the glycidyl ethers but generate highly crosslinked networks due to their higher functionality.

[007] Other oxirane-containing compounds are much slower reacting compared to aromatic glycidyl ethers or aromatic glycidyl amines when reacting with the same curatives (e.g., amine- based curatives) discussed above. For example, glycidyl ethers of aliphatic alcohols (Structure I where R¹ is a linear or branched aliphatic group) and glycidyl esters of aliphatic acids (Structure III, below, where R² is a linear or branched aliphatic residue) are much slower reacting (e.g., curing in a time that is about 2 or more, 3 or more, 4 or more, or even 5 or more times greater, depending on the specific curative used), at ambient temperature, by addition with amines or by homopolymerization compared to aromatic glycidyl ethers or aromatic glycidyl amines.

III

[008] Curing time is a particularly relevant property in manufacturing applications where the material is used in adhesives. Ambient temperature curing can provide benefits over curing at elevated temperatures such as eliminating extra baking steps, energy savings, cost savings, ability to cure when there is no oven available, and avoiding damage to substrates. While some ambient temperature cure adhesives are known, they generally do not provide rapid curing times. Longer wait times for curing lengthens the manufacturing process and risks movement of adhered substrates prior to full cure. While some rapid cure adhesives are known (e.g., so-called “5-minute epoxies”), they are typically not used in manufacturing applications for their lack of at least some desirable properties (e.g., peel resistance).

[009] The oxirane-containing compounds of Structures I, II, and III are typically synthesized by the reaction of epichlorohydrin with a hydroxy-/carboxyl-/amine-containing molecule (i.e., molecules with active hydrogens). However, epichlorohydrin, like other halogen-containing materials, is a known hazardous material associated with nasal and respiratory irritation and/or illness. Accordingly, there are few companies that work with epichlorohydrin and thus, compounds derived from the same can be costly. There remains a desire in the chemical industry to reduce or possibly even eliminate health hazards realized in synthesis, blending, and end use.

[0010] One alternative to synthesis with epichlorohydrin is the peroxyacid epoxidation of carboncarbon double bonds, which is comparatively safer than the use of epichlorohydrin and simpler to manufacture. However, the products of peroxyacid epoxidation are completely non-reactive (i.e. , not curing at all) or nearly completely non-reactive (i.e., not curing in a time of 24 hours or less) compared to glycidyl ethers, glycidyl amines, and glycidyl esters, whether aromatic or aliphatic. For example, aliphatic disubstituted oxirane rings (Structure IV, below, where R⁴ and R⁵ are linear or branched aliphatic groups) are completely non-reactive or nearly completely non-reactive to amine addition reactions at ambient temperature.

IV

[0011] Concerns over environmental renewability and sustainability have risen in recent years, not only in the chemical industry. In this regard, bio-based and/or bio-renewable reactants are highly desirable. However, the use of these types of epoxy resins derived through peroxyacid epoxidation (e.g., in adhesives) is frustrated by their complete non-reactivity or nearly complete non-reactivity as described above.

[0012] There is a need for curatives capable of curing, at ambient temperature, oxirane- containing materials in about 2 hours or less, more preferably about 1 hour or less, more preferably about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less.

[0013] There is a need for curatives capable of curing, at ambient temperature, oxirane- containing materials without charring the same (e.g., by exothermically heat).

[0014] There is a need for adhesives (e.g., two-part compositions) that provide favorable physical properties over conventional rapid cure adhesives.

[0015] There is a need for adhesives (e.g., two-part compositions) derived from oxirane- containing materials made through peroxyacid epoxidation (e.g., aliphatic disubstituted oxiranes) such that epichlorohydrin can be eliminated from their synthesis and accordingly as a possible residue in end products.

[0016] There is a need for adhesives (e.g., two-part compositions) derived from bio-based and/or bio-renewable reactants such as unsaturated natural oils, which in turn can provide high compositional percentages of bio-based ingredients. SUMMARY

[0017] The present teachings provide for a two-part composition (two-component composition), for forming an adhesive that may address at least some of the needs identified above. The two- part composition may comprise a first part (first component) comprising an aliphatic disubstituted oxirane, and a second part (second component) comprising an acidic phosphorous curative. The two-part composition may cure at a temperature of about 0 °C to 50 °C (e.g., ambient temperature (i.e., about 20 °C to 25 °C)) and after mixing the first and second parts with one another. The two- part composition may cure in about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less.

[0018] The aliphatic disubstituted oxirane may be derived from peroxyacid epoxidation. The aliphatic disubstituted oxirane may be substituted with linear and/or branched groups. The aliphatic disubstituted oxirane may have a functionality of greater than 2. The aliphatic disubstituted oxirane may be derived from peroxyacid epoxidation of (i) an unsaturated natural oil, preferably a polyunsaturated natural oil, and/or (ii) an elastomer.

[0019] The natural oil may include linseed oil and/or soybean oil.

[0020] The elastomer may include polybutadiene and/or natural rubber.

[0021] The acidic phosphorous curative may include a mineral acid, an organic phosphorous compound, or a blend of both. The mineral acid may include phosphoric acid, polyphosphoric acid, hypophosphoric acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof. The organic phosphorous compound may include an alcohol derived phosphate ester, an aliphatic epoxy-derived phosphate ester, an aromatic epoxy-derived phosphate ester, or any combination thereof.

[0022] The alcohol derived phosphate ester, the aliphatic epoxy-derived phosphate ester, and the aromatic epoxy-derived phosphate ester may be monofunctional or polyfunctional, preferably polyfunctional. Both the aliphatic disubstituted oxirane and the acidic phosphorous curative may be polyfunctional.

[0023] The alcohol derived phosphate ester may be formed from reaction of n-butanol with polyphosphoric acid. The aliphatic epoxy-derived phosphate ester may be formed from the reaction of 2-ethylhexyl glycidyl ether with phosphoric acid. The aromatic epoxy-derived phosphate ester may be formed from reaction of phenyl glycidyl ether with phosphoric acid. These phosphate esters were used in the examples provided but the range of phosphate esters that can be produced from alcohols and epoxy resins is extensive and there are few limitations on the types of phosphate esters that can be used according to the invention. [0024] The aliphatic disubstituted oxirane and the acidic phosphorous curative may be mixed in a stoichiometric ratio of about 1.5:1 to 1 :1.5, more preferably about a 1:1 stoichiometric ratio. [0025] The two-part composition may be a thermoset.

[0026] The two-part composition may further comprise a foaming agent.

[0027] The present teachings provide for a two-part composition, for forming an adhesive, that may address at least some of the needs identified above. The two-part composition may comprise a first part comprising an oxirane-containing compound, and a second part comprising an acidic phosphorous curative. The two-part composition may gel, at a temperature of about 0 °C to 50 °C (e.g., ambient temperature (i.e. , about 20 °C to 25 °C)) and upon mixing the oxirane-containing compound and the acidic phosphorous curative (after mixing the first and second part with one another). The two-part composition may gel in about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less.

[0028] The oxirane-containing compound may include a difunctional aromatic glycidyl ether, a polyfunctional aromatic glycidyl ether, a difunctional aliphatic glycidyl ether, a difunctional aliphatic glycidyl ester, a polyfunctional aromatic glycidyl amine, a polyfunctional aliphatic glycidyl ether, a polyfunctional peroxyacid epoxy, or any combination thereof.

[0029] The difunctional aromatic glycidyl ether may be a bisphenol F epoxy resin and/or a bisphenol An epoxy resin. The polyfunctional aromatic glycidyl ether may be an epoxy phenol novolac resin. The difunctional aliphatic glycidyl ether may be a glycidyl ether of butanediol. The difunctional aliphatic glycidyl ester may be a glycidyl ester of a dimer fatty acid. The polyfunctional aromatic glycidyl amine may be a glycidyl amine of methylene dianiline. The polyfunctional aliphatic glycidyl ether may be a glycidyl ether of castor oil. The polyfunctional peroxyacid epoxy may be derived from peroxyacid epoxidation of an unsaturated natural oil, preferably a polyunsaturated natural oil, and/or an elastomer.

[0030] The polyunsaturated natural oil may include linseed oil and/or soybean oil. The elastomer may include polybutadiene and/or natural rubber.

[0031] The polyfunctional peroxyacid epoxy may have a functionality of greater than 2.

[0032] The acidic phosphorous curative may include a mineral acid, an organic phosphorous compound, or a blend of both.

[0033] The mineral acid may include phosphoric acid, polyphosphoric acid, hypophosphoric acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof. The organic phosphorous compound may include an alcohol derived phosphate ester, an aliphatic epoxyderived phosphate ester, an aromatic epoxy-derived phosphate ester, or any combination thereof. [0034] The organic phosphorous compound may be monofunctional or polyfunctional, preferably polyfunctional. Both the oxirane-containing compound and the acidic phosphorous curative may be polyfunctional.

[0035] The alcohol derived phosphate ester may be formed from reaction of n-butanol with polyphosphoric acid.

[0036] The aliphatic epoxy-derived phosphate ester may be formed from reaction of 2-ethylhexyl glycidyl ether with phosphoric acid. The aromatic epoxy-derived phosphate ester may be formed from reaction of phenyl glycidyl ether with phosphoric acid.

[0037] The oxirane-containing compound and the acidic phosphorous curative may be mixed in a stoichiometric ratio of about 1.5:1 to 1 :1.5, more preferably about a 1:1 stoichiometric ratio.

[0038] The two-part composition may be a thermoset.

[0039] The two-part composition may further comprise a foaming agent.

DETAILED DESCRIPTION

[0040] The present teachings meet one or more of the above needs by the improved two-part system 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 below 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. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

[0041] The present teachings provide for a two-part composition comprising one or more oxirane- containing compounds and cures at a temperature of about 0 °C to 50 °C (e.g., ambient temperature (i.e., about 20 °C to 25 °C)).

[0042] The present teachings may find particular application with oxirane-containing compounds that are non-reactive or substantially non-reactive at ambient temperature with conventional amine-based curing agents. For instance, at ambient temperature, aliphatic disubstituted oxiranes are known to be completely non-reactive (i.e., not curing at all) or nearly completely non-reactive (i.e., not curing in a time of 24 hours or less) with conventional curatives, such as amines. [0043] The present teachings may further find application with oxirane-containing compounds that are slow-reacting at ambient temperature. For example, glycidyl ethers of aliphatic alcohols and glycidyl esters of aliphatic acids may cure with conventional amine-based curatives in about 6 hours or more, 10 hours or more, 14 hours or more, or even 18 hours or more, rendering them impractical for many purposes.

[0044] The present teachings may even find application with oxirane-containing compounds that are fast reacting at ambient temperature. For example, while aromatic glycidyl ethers can cure, with conventional amine-based curatives, in 5 hours or less, 4 hours or less, 3 hours or less, or even 2 hours or less, the curatives of the present teachings may provide for curing in minutes rather than hours.

[0045] The adhesive of the present teachings may realize an ambient temperature cure in less than 24 hours. The cure time may be about 2 hours or less, more preferably about 1 hour or less, more preferably about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less. “Rapid” as referred to herein may encompass any of these aforementioned cure times.

[0046] The adhesive cure time may be suitable for high throughput manufacturing processes (e.g., vehicle manufacturing), whereby the assembly fixture time does not have to be prolonged to wait for an adhesive to cure. Moreover, the adhesive of the present teachings may be formulated to foam (i.e., volumetrically expand). Accordingly, the rapid cure time of the present adhesive may find benefits in foaming applications whereby the adhesive cures before loss of trapped air volume and/or sagging can occur.

[0047] Cure, as referred to herein, may mean a polymerization reaction of linear chain extension and/or cross-linking such that the material being cured increases in viscosity, hardens, solidifies, or any combination thereof. Curing may also be referred to herein as gelation.

[0048] Foam, as referred to herein, may mean the generation of gas (e.g., via a foaming agent or otherwise referred to as a blowing agent) within the material such that the material expands (e.g., a volumetric expansion of about 50% to 2,000%). The polymer matrix may trap the gas therewithin. Curing of the material may cooperate with foaming such that the volumetric expansion is fixed by the curing. In this regard, the activation of curing and foaming may be selected to cooperate. The curing and foaming may occur at different times or at substantially the same time. [0049] The present teachings contemplate a relatively fast curing time, foaming time, or both as compared to other curatives or systems of curatives that function without the addition of a stimulus (e.g., heat). [0050] Foaming, if present, may begin before complete cure of the resulting reaction product. The foaming time (i.e., the time frame within which the adhesive actively foams) of the reaction product may be 30 minutes or less, 20 minutes or less, or even 10 minutes or less. The foaming time of the reaction product may be about 1 minute or more or even 5 minutes or more.

[0051] The adhesive may cure a temperature of about 0 °C to 50 °C. Curing of the adhesive may activate at ambient temperature. Volume expansion, if desired, may increase by increasing the temperature of the adhesive and/or the temperature of first and/or second parts of a two-part composition at the time of mixing.

[0052] The adhesive of the present teachings may be a two-part composition, whereby a first part is mixed with a second part, typically at the time of application upon a substrate. The reaction product, as referred to herein, may be completely cured (i.e., undergoing no further cross-linking reactions). Curing may initiate upon or after mixing the first part with the second part. Curing may initiate generally immediately after mixing the first and second parts. Curing may be delayed for a time after mixing the first and second parts.

[0053] The ambient temperature cure of oxirane-containing compounds may be achieved by reaction with one or more acidic phosphorous curatives. The first part may comprise one or more oxirane-containing compounds and the second part may comprise one or more acidic phosphorous curatives. Further, each part of the two-part composition may comprise one or more additives for modifying the properties of the adhesive.

[0054] Curing may be attributed to the chemical reaction between oxirane-containing compounds and acidic phosphorous curatives. Thus, mixing the first and second parts may initiate curing. The acidic phosphorous curatives of the present teachings may react to crosslink oxirane-containing compounds, chain extend oxirane-containing compounds, or both.

[0055] The adhesive may be a thermoplastic or a thermoset. The thermoset may be characterized by a network of crosslinking. The degree of crosslinking may be modulated by adjusting the functionality of the oxirane-containing compounds, the acidic phosphorous curatives, or both. It is contemplated by the present teachings that metal carbonate, if included in the composition, may affect the degree of cross-linking by neutralizing some of the acid component of the second part. The thermoset may be realized by selecting oxirane-containing compounds, acidic phosphorous curatives, or both with functionalities of greater than 2. Preferably, the adhesive may be a thermoset.

[0056] Properties (e.g., peel resistance) of the adhesive may be modulated by the presence of one or more copolymers with the oxirane-containing compounds, selection of desirable functional groups of the oxirane-containing compounds, the presence of one or more additives, or any combination thereof.

[0057] The oxirane-containing compounds (e.g., aliphatic disubstituted oxiranes) may be formed by peroxyacid epoxidation. In this regard, the process of forming the aliphatic disubstituted oxiranes may be free or substantially free of epichlorohydrin, and end products may be free of epichlorohydrin residues therein. The present teachings contemplate that the composition may comprise oxirane-containing compounds derived from peroxyacid epoxidation and oxirane- containing compounds derived from epichlorohydrin.

[0058] The oxirane-containing compounds (e.g., aliphatic disubstituted oxiranes) and/or acidic phosphorous curatives may be derived from bio-based and/or bio-renewable sources. For example, aliphatic disubstituted oxiranes may be derived from natural oils.

[0059] Oxirane-containing compounds.

[0060] The oxirane containing compounds described below are exemplary and are useful to teach the embodiments of the invention. They are not intended to limit the scope of the invention. It will become apparent that the teachings of the invention apply to a broad range of oxirane compounds as well as acidic phosphorus curatives.

[0061] The adhesive may comprise one or more oxirane-containing compounds. While several additional benefits may be attributed to the aliphatic disubstituted oxiranes described herein, faster curing times may be realized, relative to conventional amine-based curatives, for a wide range of oxirane-containing compounds.

[0062] The polymer network formed by the oxirane-containing compounds may provide structural and physical properties of the adhesive. Additional properties may be imparted to the adhesive by the inclusion of one or more copolymers, additives, or both. Where the adhesive is foamed, the polymer network formed by the oxirane-containing compounds may trap gas therein.

[0063] The oxirane-containing compounds may include difunctional aromatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, difunctional aliphatic glycidyl ethers, difunctional aliphatic glycidyl esters, polyfunctional aromatic glycidyl amines, polyfunctional aliphatic glycidyl ethers, aliphatic disubstituted oxiranes, or any combination thereof.

[0064] The adhesive may comprise one or more difunctional aromatic glycidyl ethers. The glycidyl ethers may be characterized by Structure I, herein,

I wherein R¹ comprises aromatic groups but no additional oxiranes. [0065] The difunctional aromatic glycidyl ether may have an epoxy equivalent weight of about 140 g/eq or more, 150 g/eq or more, or even 160 g/eq or more (as measured according to ASTM D1652 - 11). The difunctional aromatic glycidyl ether may have an epoxy equivalent weight of about 200 g/eq or less, 190 g/eq or less, 180 g/eq or less, or even 170 g/eq or less (as measured according to ASTM D1652 - 11).

[0066] The difunctional aromatic glycidyl ether may have a viscosity, at ambient temperature, of about 1,500 cPs or more, 2,000 cPs or more, 2,500 cPs or more, or even 3,000 cPs or more (as measured according to ASTM D2393-86). The difunctional aromatic glycidyl ether may have a viscosity, at ambient temperature, of about 5,500 cPs or less, 5,000 cPs or less, 4,500 cPs or less, 4,000 cPs or less, or even 3,500 cPs or less (as measured according to ASTM D2393-86).

[0067] The difunctional aromatic glycidyl ether may include bisphenol F epoxy resin. An exemplary bisphenol F epoxy resin may include Epokukdo YDF-170, commercially available from Kukdo Chemical Co., Ltd.

[0068] The difunctional aromatic glycidyl ether may include bisphenol A epoxy resin. An exemplary bisphenol A epoxy resin may include Epokukdo YD-128, commercially from Kukdo Chemical Co., Ltd.

[0069] The adhesive may comprise one or more polyfunctional aromatic glycidyl ethers. The polyfunctional aromatic glycidyl ethers may be characterized by Structure I, herein, wherein R¹ comprises aromatic groups and additional oxiranes. The polyfunctional aromatic glycidyl ether may have a functionality of about 2.3 to 3.0 (e.g., 2.6).

[0070] The polyfunctional aromatic glycidyl ether may have an epoxy equivalent weight of about 150 g/eq or more, 155 g/eq or more, 160 g/eq or more, or even 165 g/eq or more (as measured according to ASTM D1652 - 11). The polyfunctional aromatic glycidyl ether may have an epoxy equivalent weight of about 185 g/eq or less, 180 g/eq or less, 175 g/eq or less, or even 170 g/eq or less (as measured according to ASTM D1652 - 11).

[0071] The polyfunctional aromatic glycidyl ether may have a viscosity, at ambient temperature, of about 16,000 cPs or more, 17,000 cPs or more, 18,000 cPs or more, 19,000 cPs or more, or even 20,000 cPs or more (as measured according to ASTM D2393 - 86). The polyfunctional aromatic glycidyl ether may have a viscosity, at ambient temperature, of about 25,000 cPs or less, 24,000 cPs or less, 23,000 cPs or less, 22,000 cPs or less, or even 21 ,000 cPs or less (as measured according to ASTM D2393 - 86).

[0072] The polyfunctional aromatic glycidyl ether may include epoxy phenol novolac resin. An exemplary epoxy phenol novolac resin may include DEN 426, commercially available from Olin Corporation. [0073] The adhesive may comprise one or more difunctional aliphatic glycidyl ethers. The difunctional aliphatic glycidyl ethers may be characterized by Structure I, herein, wherein R¹ is aliphatic and comprises no additional oxiranes.

[0074] The difunctional aliphatic glycidyl ether may have an epoxy equivalent weight of about 110 g/eq or more, 115 g/eq or more, 120 g/eq or more, or even 125 g/eq or more (as measured according to ASTM D1652 - 11). The difunctional aliphatic glycidyl ether may have an epoxy equivalent weight of about 150 g/eq or less, 145 g/eq or less, 140 g/eq or less, or even 135 g/eq or less (as measured according to ASTM D1652 - 11).

[0075] The difunctional aliphatic glycidyl ether may include diglycidyl ether of butanediol. An exemplary diglycidyl ether of butanediol may include KF Epiol DE200, commercially available from Kukdo Chemical.

[0076] The adhesive may comprise one or more difunctional aliphatic diglycidyl esters. The difunctional aliphatic diglycidyl esters may be characterized by Structure III, herein, wherein R² is aliphatic and comprises no additional oxiranes.

[0077] The difunctional aliphatic glycidyl ester may have an epoxy equivalent weight of about 380 g/eq or more, 390 g/eq or more, 400 g/eq or more, 410 g/eq or more, or even 420 g/eq or more (as measured according to ASTM D1652 - 11). The difunctional aliphatic diglycidyl ester may have an epoxy equivalent weight of about 480 g/eq or less, 470 g/eq or less, 460 g/eq or less, 450 g/eq or less, or even 440 g/eq or less (as measured according to ASTM D1652 - 11).

[0078] The difunctional aliphatic glycidyl ester may have a viscosity, at ambient temperature, of about 300 cPs or more, 400 cPs or more, or even 500 cPs or more (as measured according to ASTM D2393 - 86). The difunctional aliphatic diglycidyl ester may have a viscosity, at ambient temperature, of about 1,000 cPs or less, 900 cPs or less, 800 cPs or less, or even 700 cPs or less (as measured according to ASTM D2393 - 86).

[0079] The difunctional aliphatic diglycidyl ester may include a diglycidyl ester of a dimer fatty acid. An exemplary diglycidyl ester of a dimer fatty acid may include Epokukdo YD-171 , commercially available from Kukdo Chemical.

[0080] The adhesive may comprise one or more polyfunctional aromatic glycidyl amines. The polyfunctional aromatic glycidyl amines may be characterized by Structure II, wherein R³ comprises aromatic groups.

[0081] The polyfunctional aromatic glycidyl amine may have an epoxy equivalent weight of about 100 g/eq or more, 105 g/eq or more, or even 110 g/eq or more (as measured according to ASTM D1652 - 11). The polyfunctional aromatic glycidyl amine may have an epoxy equivalent weight of about 130 g/eq or less, 125 g/eq or less, or even 120 g/eq or less (as measured according to ASTM D1652 - 11).

[0082] The polyfunctional aromatic glycidyl amine may have a viscosity, at 50°C, of about 2,500 cPs or more, 3,000 cPs or more, 3,500 cPs or more, or even 4,000 cPs or more (as measured according to ASTM D2393 - 86). The polyfunctional aromatic glycidyl amine may have a viscosity, at 50°C, of about 7,000 cPs or less, 6,500 cPs or less, 6,000 cPs or less, 5,500 cPs or less, or even 5,000 cPs or less (as measured according to ASTM D2393 - 86).

[0083] The polyfunctional aromatic glycidyl amine may include a glycidyl amine of methylene dianiline. An exemplary glycidyl amine of methylene dianiline may include Epotec YDM-441 , commercially available from Azelis.

[0084] The adhesive may comprise one or more polyfunctional aliphatic glycidyl ethers. The polyfunctional aliphatic glycidyl ethers may be characterized by Structure I, where R¹ is aliphatic and is capable of being epoxidized at multiple sites.

[0085] The polyfunctional aliphatic glycidyl ethers may have an epoxy equivalent weight of about 450 g/eq or more, 500 g/eq or more, or even 550 g/eq or more (as measured according to ASTM D1652 - 11). The polyfunctional aliphatic glycidyl ether may have an epoxy equivalent weight of about 700 g/eq or less, 650 g/eq or less, or even 600 g/eq or less (as measured according to ASTM D1652 - 11).

[0086] The polyfunctional aliphatic glycidyl ethers may include a glycidyl ether of castor oil. An exemplary polyfunctional glycidyl ether of castor oil may include Kukdo PE-412, commercially available from Kukdo Chemical. The polyfunctional aliphatic glycidyl ethers may include the triglycidyl ether of glycerol. An exemplary triglycidyl ether or glycerol includes Erysis GE-38 available from Huntsman.

[0087] The adhesive may comprise one or more polyfunctional peroxyacid epoxies. The polyfunctional peroxyacid epoxies may be advantageous for their low cost, wide availability, simple production method, and applicability of peroxyacid epoxidation to a wide range of organic compounds having unsaturated carbon-carbon double bonds.

[0088] The polyfunctional peroxyacid epoxies may include aliphatic disubstituted oxiranes. The aliphatic disubstituted oxiranes may be derived from peroxyacid epoxidation. The aliphatic disubstituted oxiranes may be substituted with linear and/or branched groups. The aliphatic disubstituted oxiranes may include those following Structure IV, herein, where R⁴ and R⁵ are linear and/or branched aliphatic groups that also contain oxirane rings. It is also anticipated that the one or more oxirane rings on the polyfunctional peroxyacid epoxies may be terminal to the compound, such the R⁴ or R⁵ are H-atoms. An exemplary oxirane compound of this type is 1 ,7- octadiene diepoxide. Terminal epoxide groups may be expected to be slightly more reactive than disubstituted groups. Another special class of peracid epoxies are the cycloaliphatic epoxies where the oxirane ring is formed on a cyclohexene ring, creating a bicyclic compound with additional ring strain in the oxirane ring. An exemplary compound of this type is (3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), available as Syna 21 from Synasia, Inc. Because of ring strain, these compounds do react with conventional amine curatives but only slowly. However, they react rapidly with the acidic phosphorus curatives of the disclosed invention.

[0089] The aliphatic disubstituted oxirane may comprise two or more oxirane groups (i.e., have a functionality equal to or greater than 2). In this regard, with a functionality of at least 2, extended polymer chains may be formed, and with a functionality of greater than 2, crosslinking may be realized.

[0090] The aliphatic disubstituted oxirane may be derived from peroxyacid epoxidation of an unsaturated natural oil and/or an elastomer. Preferably, the natural oil is a polyunsaturated natural oil, although the present teachings contemplate any suitable polyunsaturated natural oil subject to peroxyacid epoxidation.

[0091] Examples of natural oils may include linseed oil, soybean oil, cashew nut shell liquid (“CNSL”), tall oil, the like, or any combination thereof. Peroxyacid epoxidation of linseed oil gives rise to “epoxidized linseed oil” (“ELO”). Peroxyacid epoxidation of soybean oil gives rise to “epoxidized soybean oil” (“ESO”). Peroxyacid epoxidation of cashew nutshell liquid gives rise to “epoxidized cashew nut shell liquid (“ECNSL”).

[0092] The natural oil may be monounsaturated (e.g., tall oil and CNSL) or polyunsaturated (e.g., linseed oil and soybean oil), where each site of unsaturation provides for an epoxy group site. Preferably, the natural oil is polyunsaturated if higher amounts of cross-linking are desired. The present teachings contemplate that a blend of monounsaturated and polyunsaturated natural oils may be employed. While not providing for cross-linking, the monounsaturated natural oils may function as reactive plasticizers.

[0093] The epoxidized natural oils may be bio-based and/or bio-renewable. That is, the natural oils may be extracted from natural sources.

[0094] Epoxidized natural oils are conventionally available as stabilizers in chlorinated polymers (e.g., polyvinyl chloride). However, conventional use in adhesives is limited due to relatively slow or possibly no reactivity with conventional epoxy curatives including amine-based curatives which constitute the largest group of room temperature epoxy curatives. Without intending to be bound by theory, the reactivity may be due to incompatibility of the hydrophobic epoxidized natural oils with polar nitrogen groups in such curatives. However, the products of peroxyacid epoxidation discussed herein (see, e.g., Structure IV) may have no proximal heteroatoms.

[0095] The polyfunctional peracid epoxy may also include peracid epoxidized liquid, semisolid or solid unsaturated elastomers. The elastomers may include lower molecular weight liquid elastomers and/or solid or semi-solid elastomers. The liquid elastomers may be liquid and flow at ambient temperature. The solid or semi-solid elastomers may be solid and do not flow at ambient temperature or are viscoelastic at ambient temperature. The elastomers may impart flexibility into the cured adhesive.

[0096] The peracid epoxidize elastomer may include polybutadiene and/or natural rubber. The peracid epoxidized polybutadiene may be liquid, semisolid or solid. Polybutadiene may be advantageous for providing a high density of oxirane groups by peroxyacid epoxidation.

[0097] The aliphatic disubstituted oxirane may have an ambient temperature viscosity of about 600 cPs or more, 650 cPs or more, or even 700 cPs or more (as measured according to ASTM D2393 - 86). The aliphatic disubstituted oxirane may have an ambient temperature viscosity of about 900 cPs or less, 950 cPs or less, 800 cPs or less, 750 cPs or less (as measured according to ASTM D2393 - 86).

[0098] The aliphatic disubstituted oxirane may have an oxirane oxygen content of about 6 or more, 7 or more, or even 8 or more percent by weight. The aliphatic disubstituted oxirane may have an oxirane oxygen content of about 11 or less, 10 or less, or even 9 or less percent by weight.

[0099] An exemplary aliphatic disubstituted oxirane may include Epoxol® 9-5 (a bio-based high oxirane epoxidized linseed oil), commercially available from ACS Technical Products.

[00100] Acidic phosphorous curative.

[00101] The adhesive may comprise one or more acidic phosphorous curatives. Theacidic phosphorous curatives may provide for a cure time that is commercially useful. The acidic phosphorous curatives may provide for a cure time of the adhesive of about 2 hours or less, more preferably about 1 hour or less, more preferably about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less.

[00102] The acidic phosphorous curatives of the present teachings may react with oxirane- containing compounds that are completely unreactive or substantially unreactive to conventional alkaline epoxy curatives based on amine hydrogens or amine derived curatives based on nitrogen. [00103] The acidic phosphorous curatives of the present teachings may react faster, relative to alkaline epoxy curatives, with many oxirane-containing compounds that do react with alkaline epoxy curatives based on amine hydrogens or curatives based on nitrogen (e.g., oxirane- containing compounds including glycidyl ethers, glycidyl esters, and glycidyl amines, whether aromatic or aliphatic).

[00104] The acidic phosphorous curatives may provide for crosslinking, homopolymerization, or both.

[00105] The acidic phosphorous curatives may include oxidized phosphorous and contain an acidic hydroxyl group. The acidic hydroxyl group may be capable of ionizing in the presence of moisture. The acidic phosphorous curative may comprise at least one ionizable -POH group, as shown below.

[00106] For effective formation of a three-dimensional crosslinked network, preferably the acidic phosphorus curative may have an average functionality of greater than 2. This can be achieved by utilization of blends of acidic phosphorous curatives. For example, a monophosphate ester of phosphoric acid, containing two ionizable -POH groups can be blended with phosphoric acid to give a curative mixture with an average functionality of between 2 and 3 depending on the ratio utilized. Alternatively, a difunctional or even a monofunctional acidic phosphorous curative could be blended with a polyfunctional acidic phosphorous curative to provide a curative with an average functionality of greater than 2.

[00107] Acidic phosphorous curatives with functionalities as high as 3, 4, 5, or even higher can be obtained by the reaction of di-, tri-, or even higher functional alcohols with P₂O₅ or polyphosphoric acid. Similarly, di-, tri-, or higher functionality epoxides can be reacted with phosphoric acid to obtain acidic phosphorous compounds with a higher number functionality of acidic -POH groups.

[00108] The acidic phosphorous curatives may include mineral acids, organic phosphorous compounds, or both.

[00109] The mineral acids may include phosphoric acid (H3PO4), polyphosphoric acid, hypophosphoric acid, (H4P2O6), pyrophosphoric acid (H4P2O7), phosphonic acid (H2PO3), phosphinic acid (H3PO2), or any combination thereof. [00110] The organic phosphorous compounds may include alkyl and aryl esters of phosphoric acid, alkyl or aryl phosphonates, dialkyl or diaryl phosphinates, or any combination thereof.

[00111] Preferred organic phosphorous compounds may include esters of phosphoric acid. Esters of phosphoric acid typically have a lower cost and ease of synthesis relative to other acidic phosphorous compounds.

[00112] The organic phosphorous compounds may be selected from mono-esters or diesters, as shown below: mono-ester Di-ester Tri-ester

[00113] The present teachings contemplate that the composition may comprise tri-esters, as shown above. Although typically not reactive, residues of tri-esters may be present as reaction byproducts in the synthesis of the organic phosphorous compounds or added as a mixture with the mono-esters and/or di-esters.

[00114] The organic phosphorous compounds may be obtained from the reaction of epoxide groups with phosphoric acid as depicted below: [00115] Substitution (e.g., to form esters) may also reduce the functionality of the curative and result in reduced crosslink density and accordingly, lower modulus, higher strain to failure, lower glass transition temperature, increased fracture energy, or any combination thereof. Substitution may also incorporate moieties for imparting other favorable properties to the cured composition.

[00116] Substituted organic phosphorous compounds (e.g., monoesters of phosphoric acid) may be desirable for crosslinking reactions, either alone or in a blend with mineral acids. In this regard, mineral acids can exhibit fast reaction rates resulting in excess exothermic energy release, which could char the adhesive. Thus, blending with substituted organic phosphorous compounds may mitigate the excess exothermic energy release that may be realized by using mineral acids alone.

[00117] The esters of phosphoric acid may be produced by the reaction of alcohols with phosphorous pentoxide (P2O5), polyphosphoric acid, or orthophosphoric acid. The esters of phosphoric acid may have a high percentage of monoester and low free phosphoric acid content. The esters of phosphoric acid may have an excess of free phosphoric acid. The esters of phosphoric acid may be synthesized to provide for the free phosphoric acid content or can be included in blends of phosphoric acid.

[00118] Exemplary organic phosphorous compounds may include those characterized by the Structures V, VI, and VII, below.

[00119] Structure V, below, shows the monobutyl phosphate ester of phosphoric acid formed by the reaction of n-butanol with a slight stochiometric excess of polyphosphoric acid.

V

[00120] Phosphate esters can also be synthesized through the reaction of epoxies with excess phosphoric acid as described in U.S. Patent No. 10,550,220 B2, incorporated herein by reference in its entirety for all purposes. For example, Structure VI, below, is formed by the reaction of the 2-ethylhexyl glycidyl ether with a slight excess of 85% phosphoric acid. [00121] Similarly, Structure VII is formed by the reaction of phenyl glycidyl ether with a slight excess of 85% phosphoric acid.

[00122] Foaming may be achieved by the presence of one or more metal carbonates, blowing agents, or both in the adhesive. Metal carbonates (e.g., calcium carbonate) may be preferred for their reactivity with the acidic phosphorous curatives of the present teachings. The present teachings contemplate that blowing agents such as physical blowing agents and/or chemical blowing agents. The physical blowing agents and/or chemical blowing agents may be present with the metal carbonates.

[00123] Examples of suitable chemical blowing agents may include dinitrosopentamethylenetetrarnine, azodicarbonamide, dinitroso-pentamethylenetetramine, 4,4'oxy-bis-(benzene-sulphonyihydrazide), trihydrazinotriazine, N,N'-dimethyl-N,N'-dinitroso- terephthalamide, or any combination thereof.

[00124] Examples of suitable physical blowing agents may include physical blowing agents sold under the tradename Expancel®, commercially available from Akzo Nobel.

[00125] Examples of suitable metal carbonates may include the calcium carbonates of Hubercarb® Q2, Q4, Q200 or Q325 from Huber Engineered Materials.

[00126] The metal carbonates, blowing agents, or both may be present in an amount of about 10% or less, 8% or less, 6% or less, 4% or less, or even 2% or less, by weight. Where metal carbonates are employed, they may be present in the first side as they are reactive with the second side. The blowing agents may be present in the first and/or second sides.

[00127] The adhesive may include one or more functional additives for improving one or more various properties of the composition. Examples of suitable functional additives may include toughening agents (e.g., core-shell polymeric particles), reinforcing fiber, antioxidants, antiozonants, ultraviolet absorbers, thixotropes, antistatic agents, colorants, coupling agents, curing agents, flame retardants, minerals, blowing agents, heat stabilizers, impact modifiers, lubricants, plasticizers, preservatives, processing aids, stabilizers, the like, and any combination thereof. The additives may be present in the first and/or second parts of the adhesive.

[00128] Examples. [00129] The materials used in the examples below are described in Table 1. These include oxirane-containing compounds as described herein, both those derived from epichlorohydrin to form glycidyl ethers, amines, and esters as well as those derived from peroxyacid epoxidation of carbon-carbon double bonds. Also described in Table 1 are conventional amine-based curatives and acid phosphorous curatives.

[00130] Table 1.

[00131] Table 2, below, shows the gelation times (reported in minutes) for the reactions of various oxirane-containing compounds with both conventional amine curatives (e.g., aliphatic amines, cycloaliphatic amines, tertiary amines, polyamides, and amidoamines) and acidic phosphorous curatives according to the present teachings.

[00132] Sample preparation. Samples were prepared by mixing a 1 :1 stoichiometric ratio of oxirane groups to either amine hydrogen groups (-NH) or acidic phosphorous groups (-POH) to realize a 30-gram mass of combined oxirane-containing compound and curative. The exception is for the tertiary amines, which contains neither reactive amine hydrogen groups nor acid phosphorus groups. In this case, each oxirane-containing compound was mixed with the tertiary amine at a ratio of 3.1 equivalents of oxirane groups to 1 equivalent of tertiary amine groups (e.g., equating to a mix ratio of 15 phr (parts per hundred resin) if mixing the tertiary amine with a liquid bisphenol An epoxy resin having an epoxy equivalent weight (“EEW”) of 190 grams per equivalent).

[00133] Test procedure. Gel times were measured using the Hot Pot Gel Timer (Article No.: 11576, commercially available from Gardco). The first and second parts were each loaded into a container and mixed with a speedmixer at 2450 RPM for 30 seconds at ambient temperature. The combined first and second parts amounted to 30 g. The 30 g mixture was then set up with the Hot Pot Gel Timer, where the test was conducted at ambient temperature and without the use of a heating element. The gel time was measured from the moment the first and second parts were mixed. Ultimately, the gel time is determined when a rotating hook being driven by the Gel Timer is seized by the fluid viscosity of the sample.

[00134] For samples which cured in less than 30 seconds in the above method, the first and second parts were hand mixed and gel times were determined by the hand mixing, when the mixing device was seized by the fluid viscosity of the sample.

[00135] Table 2.

[00136] Table 2, continued.

[00137] The aromatic glycidyl ethers (glycidyl ethers of bisphenol F and epoxy phenol novolac resin), showed the fastest curing, comparatively, with the conventional amine curatives and cure even faster with the acidic phosphorous curatives of the present teachings. This indicates the suitability of acidic phosphorous compounds for use in rapid cure systems.

[00138] A similar observation was made for the glycidyl amine (glycidyl amine of methylene dianiline). Although slower curing than the aromatic glycidyl ethers, the glycidyl amine cures in minutes when cured with the acidic phosphorous curatives rather than hours with the conventional amine curatives.

[00139] The difunctional aliphatic glycidyl ether and glycidyl ester are slower than the above with conventional amine curatives, and in the case of the amidoamine, failed to cure in 1440 minutes (24 hours). Gelation times of greater than 24 hours makes the system impractical to use in many adhesive applications. Yet these epoxy resins, in most cases, gelled within minutes with the acidic phosphorous compounds of the present teachings. The exception is for the aliphatic epoxy derived phosphate ester, which did not gel the difunctional aliphatic glycidyl ether in 24 hours or less. This combination of epoxy resin and curative did produce a significant exotherm, suggesting that a reaction did occur. The final viscosity of the reacted system was lower than the initial viscosity of the mixture suggesting the curing reaction was accompanied by a side reaction, possibly a hydrolysis reaction, which prevents the formation of a 3-dimensional network of bonds and inhibits gelation.

[00140] A polyfunctional aliphatic glycidyl ether selected for evaluation was epoxidized castor oil. It was selected because of its high bio-renewable carbon content. Unexpectedly, the epoxidized castor oil did not gel in 24 hours or less with conventional curatives. Without intending to be bound by theory, this is likely because the polyfunctional aliphatic glycidyl ether chosen has a high epoxy equivalent weight (“EEW’), resulting in a low density of reactive sites. Additionally, the aliphatic nature of the epoxidized castor oil may make it less compatible with the amine curatives, which is likely to contribute to the slow gelation. However, this slow gelling glycidyl ether gelled in less than a few hours with the acidic phosphorous curatives of the present teachings. These gelation times are sufficiently rapid for use in many thermosetting adhesive applications. Another polyfunctional glycidyl ether selected for demonstration of the invention was the triglycidyl ether of glycerol. This triglycidyl ether has a lower epoxy equivalent weight and is therefore capable of generating a higher crosslink density in a shorter time, resulting in shorter gel times.

[00141] It is significant to note that even with an amine accelerated mercaptan curing system, used in many standard fast curing epoxy systems, the peroxyacid epoxy does not gel in 1440 minutes. Yet the acidic phosphorus compounds are capable of rapidly gelling the peroxyacid epoxy.

[00142] It is demonstrated, in Table 2, that peroxyacid epoxy, in this case epoxidized linseed oil, though relatively unreactive toward conventional amine curatives and fast curing mercaptan curing systems, gels in less than a minute, when cured with the acidic phosphorous curatives of the present teachings. Without intending to be bound by theory, this rapid gelation is likely a combination of the higher functionality of the epoxidized linseed oil and the intrinsically more reactive acidic -POH groups of the curatives used.

[00143] Other strong mineral acids can induce polymerization of epoxy resins, including those resins produced through peroxyacid epoxidation. For example, 96% sulfuric acid and 70% nitric acid can induce polymerization. It should be noted however that the reaction is often quite rapid and exothermic, resulting in charring even when mixing small quantities. The reaction with a monofunctional mineral acid such as nitric acid also suggests the occurrence of some homopolymerization in acid cured epoxy systems as the monoacidic nitric acid would not otherwise be capable of inducing the formation of a three-dimensional network. The present teachings contemplate the inclusion of nitric acid to induce homopolymerization of the resins produced through peroxyacid epoxidation.

[00144] The use of phosphoric acid is preferred and the use of monoesters of phosphoric acid as curatives alone, or in combination with phosphoric acid, provides a means to moderate and control the reactivity while still allowing both chain extension and crosslinking of an epoxy resin to form a three-dimensional thermoset material.

[00145] It is understood that the above description is intended to be illustrative and not restrictive. Accordingly, the specific embodiments of the present invention as set forth are not intended as being exhaustive or limiting of the teachings. 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.

[00146] 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 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.

[00147] Plural elements can be provided by a single integrated element. Alternatively, a single element might be divided into separate plural elements. The disclosure of “a” or “one” to describe an element is not intended to foreclose additional elements.

[00148] While the terms first, second, third, etc., may be used herein to describe various components, these components should not be limited by these terms. These terms may be used to distinguish one component from another component. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first component discussed herein could be termed a second component without departing from the teachings.

[00149] The terms “generally”, “substantially”, or “about” to describe measurements, percentages, or ratios may mean +/- 10% or less, +/- 5% or less, or even +/- 1 % or less. The terms “generally”, “substantially”, or “about” to describe measurements, percentages, or ratios may mean +/- 0.01% or greater, +/- 0.1 % or greater, or even +/- 0.5% or greater.

[00150] 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.

[00151] As used herein, “aliphatic” preferably means a straight or branched hydrocarbon radical containing up to twenty four carbon atoms wherein the saturation between any two carbon atoms is a single, double or triple bond. An aliphatic group preferably contains from 1 to about 24 carbon atoms, more typically from 1 to about 12 carbon atoms with from 1 to about 6 carbon atoms being more preferred.

[00152] As used herein, “cycloaliphatic” preferably means a saturated or unsaturated, nonaromatic hydrocarbon moiety having from 1 to 3 rings, each ring having from 3 to 8 (preferably from 3 to 6) carbon atoms.

[00153] As used herein, “aromatic” preferably mean a mono- or polycyclic carbocyclic ring system radicals having one or more aromatic rings. Examples of aryl groups include without limitation, phenyl and naphthyl.

[00154] 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, from 20 to 80, or from 30 to 70, it is intended that intermediate range values such as (for example, 15 to 85, 22 to 68, 43 to 51, 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. Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. [00155] 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.”

[00156] 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 essentially of the elements, ingredients, components, or steps.

[00157] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes.

Claims

What is claimed is:

Claim 1: A two-part composition, for forming an adhesive, comprising: a first part comprising an oxirane-containing compound, and a second part comprising an acidic phosphorous curative; preferably wherein the two-part composition gels, at a temperature of about 0 °C to 50 °C (e.g., ambient temperature (i.e. , about 20 °C to 25 °C)) and upon mixing the oxirane-containing compound and the acidic phosphorous curative, in about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less.

Claim 2: The two-part composition according to Claim 1 , wherein the aliphatic disubstituted oxirane is derived from peroxyacid epoxidation.

Claim 3: The two-part composition according to Claim 1 or Claim 2, wherein the aliphatic disubstituted oxirane is substituted with linear and/or branched groups.

Claim 4: The two-part composition according to any of the preceding claims, wherein the aliphatic disubstituted oxirane has a functionality of greater than 2.

Claim 5: The two-part composition according to any of the preceding claims, wherein the aliphatic disubstituted oxirane is derived from peroxyacid epoxidation of:

(i) an unsaturated natural oil, preferably a polyunsaturated natural oil, and/or

(ii) an elastomer.

Claim 6: The two-part composition according to Claim 5, wherein the natural oil is linseed oil and/or soybean oil.

Claim 7: The two-part composition according to Claim 5 or Claim 6, wherein the elastomer includes polybutadiene and/or natural rubber.

Claim 8: The two-part composition according to any of the preceding claims, wherein the acidic phosphorous curative includes a mineral acid, an organic phosphorous compound, or a blend of both. Claim 9: The two-part composition according to Claim 8, wherein the mineral acid includes phosphoric acid, polyphosphoric acid, hypophosphoric acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof.

Claim 10: The two-part composition according to Claim 8 or Claim 9, wherein the organic phosphorous compound includes an alcohol derived phosphate ester, an aliphatic epoxy-derived phosphate ester, an aromatic epoxy-derived phosphate ester, or any combination thereof.

Claim 11 : The two-part composition according to Claim 10, wherein the alcohol derived phosphate ester, the aliphatic epoxy-derived phosphate ester, and the aromatic epoxy-derived phosphate ester are independently of one another monofunctional or polyfunctional, preferably polyfunctional.

Claim 12: The two-part composition according to any of the preceding claims, wherein both the aliphatic disubstituted oxirane and the acidic phosphorous curative are polyfunctional.

Claim 13: The two-part composition according to any of Claim 10 through Claim 12, wherein the alcohol derived phosphate ester is formed from reaction of n-butanol with polyphosphoric acid; wherein the aliphatic epoxy-derived phosphate ester is formed from reaction of 2-ethylhexyl glycidyl ether with phosphoric acid; and wherein the aromatic epoxy-derived phosphate ester is formed from reaction of phenyl glycidyl ether with phosphoric acid.

Claim 14: The two-part composition according to any of the preceding claims, wherein the aliphatic disubstituted oxirane and the acidic phosphorous curative are mixed in a stoichiometric ratio of about 1.5:1 to 1 :1.5, more preferably about a 1 : 1 stoichiometric ratio.

Claim 15: The two-part composition according to any of the preceding claims, wherein the two-part composition is a thermoset.

Claim 16: The two-part composition according to any of the preceding claims, wherein the two-part composition further comprises a foaming agent.

Claim 17: A two-part composition, comprising: a first part comprising an aliphatic disubstituted oxirane, and a second part comprising an acidic phosphorous curative; preferably wherein the two-part composition cures, at a temperature of about 0 °C to 50 °C (e.g., ambient temperature (i.e. , about 20 °C to 25 °C)) and after mixing the first and second parts, in about 10 minutes or less, more preferably about 5 minutes or less, or even more preferably about 1 minute or less.

Claim 18: The two-part composition according to claim 17, which is a two-part composition according to any of Claim 1 to Claim 16.

Claim 19: The two-part composition according to Claim 17 or Claim 18, wherein the oxirane- containing compound includes a difunctional aromatic glycidyl ether, a polyfunctional aromatic glycidyl ether, a difunctional aliphatic glycidyl ether, a difunctional aliphatic glycidyl ester, a polyfunctional aromatic glycidyl amine, a polyfunctional aliphatic glycidyl ether, a polyfunctional peroxyacid epoxy, or any combination thereof.

Claim 20: The two-part composition according to any of Claim 17 to Claim 19, wherein the oxirane-containing compound includes a difunctional aromatic glycidyl ether, which preferably is a bisphenol F epoxy resin and/or a bisphenol A epoxy resin.

Claim 21 : The two-part composition according to any of Claim 17 to Claim 20, wherein the oxirane-containing compound includes a polyfunctional aromatic glycidyl ether, which is an epoxy phenol novolac resin.

Claim 22: The two-part composition according to any of Claim 17 to Claim 21 , wherein the oxirane-containing compound includes a difunctional aliphatic glycidyl ether, which preferably is a glycidyl ether of butanediol.

Claim 23: The two-part composition according to any of Claim 17 to Claim 22, wherein the oxirane-containing compound includes a difunctional aliphatic glycidyl ester, which preferably is a glycidyl ester of a dimer fatty acid. Claim 24: The two-part composition according to any of Claim 17 to Claim 23, wherein the oxirane-containing compound includes a polyfunctional aromatic glycidyl amine, which preferably is a glycidyl amine of methylene dianiline.

Claim 25: The two-part composition according to any of Claim 17 to Claim 24, wherein the oxirane-containing compound includes a polyfunctional aliphatic glycidyl ether, which preferably is a glycidyl ether of castor oil.

Claim 26: The two-part composition according to any of Claims 17 to Claim 25, wherein the oxirane-containing compound includes a polyfunctional peroxyacid epoxy, which preferably is derived from peroxyacid epoxidation of:

(i) an unsaturated natural oil, preferably a polyunsaturated natural oil, and/or

(ii) an elastomer.

Claim 27: The two-part composition according to Claim 26, wherein the polyunsaturated natural oil is linseed oil and/or soybean oil.

Claim 28: The two-part composition according to Claim 26 or Claim 27, wherein the elastomer includes polybutadiene and/or natural rubber.

Claim 29: The two-part composition according to any of Claim 19 to Claim 28, wherein the polyfunctional peroxyacid epoxy has a functionality of greater than 2.

Claim 30: The two-part composition according to any of Claim 17 to Claim 29, wherein the acidic phosphorous curative includes a mineral acid, an organic phosphorous compound, or a blend of both.

Claim 31 : The two-part composition according to Claim 30, wherein the mineral acid includes phosphoric acid, polyphosphoric acid, hypophosphoric acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof; and wherein the organic phosphorous compound includes an alcohol derived phosphate ester, an aliphatic epoxy-derived phosphate ester, an aromatic epoxy-derived phosphate ester, or any combination thereof. Claim 32: The two-part composition according to Claim 30 or Claim 31 , wherein the organic phosphorous compound are monofunctional or polyfunctional, preferably polyfunctional.

Claim 33: The two-part composition according to any of Claim 30 to Claim 32, wherein both the oxirane-containing compound and the acidic phosphorous curative are polyfunctional.

Claim 34: The two-part composition according to any of Claim 31 to Claim 33, wherein the alcohol derived phosphate ester is formed from reaction of n-butanol with polyphosphoric acid.

Claim 35: The two-part composition according to any of Claim 31 to Claim 34, wherein the aliphatic epoxy-derived phosphate ester is formed from reaction of 2-ethylhexyl glycidyl ether with phosphoric acid; and wherein the aromatic epoxy-derived phosphate ester is formed from reaction of phenyl glycidyl ether with phosphoric acid.

Claim 36: The two-part composition according to any of Claim 17 to Claim 35, wherein the oxirane-containing compound and the acidic phosphorous curative are mixed in a stoichiometric ratio of about 1.5:1 to 1 :1.5, more preferably about a 1 : 1 stoichiometric ratio.

Claim 37: The two-part composition according to any of Claims 17 to Claim 36, wherein the two-part composition is a thermoset.

Claim 38: The two-part composition according to any of Claim 17 to Claim 38, wherein the two-part composition further comprises a foaming agent.