Room temperature rapidly curing system of oxirane-containing compounds

Abstract

An adhesive containing an oxirane-containing compound and an acidic phosphorus-based curing agent. When this adhesive is mixed with an aliphatic disubstituted oxirane at a temperature of approximately 0°C to 50°C, it gels within approximately 10 minutes.

Description

[Technical Field]

[0001] Claim of priority This application claims priority to U.S. Provisional Application No. 63 / 461,732, filed on 25 April 2023, which is incorporated herein by reference in its entirety for all purposes.

[0002] This instruction generally relates to ambient temperature curing systems, rapid cure systems, and two-part compositions formulated using them. This rapid curing system utilizes the curing reaction between an oxirane-containing compound and an acidic phosphorus-based curing agent. This instruction is particularly suitable for oxirane-containing compounds that are not derived from epichlorohydrin and which typically react too slowly with conventional epoxy curing agents to yield useful products. [Background technology]

[0003] Glycidyl ethers (structural formula I below) and glycidylamines (structural formula II below) can react and crosslink with many known curing agents at room temperature (i.e., approximately 20°C to 25°C) to form addition products. Furthermore, glycidyl ethers and glycidylamines can also be induced to undergo homopolymerization at room temperature using several known catalysts.

[0004] [ka] I [ka] II

[0005] Glycidyl ethers of aromatic phenols are particularly well-suited for crosslinking reactions, forming a three-dimensional thermosetting network. For example, diglycidyl ether of bisphenol A ("DGEBA") (R 1Structural formula I), in which is 4,4'-substituted 2,2-diphenylpropane, is known to react at room temperature with aromatic or aliphatic amines, mercaptans or thiols, acid anhydrides, and curing agents such as carboxylic acids via addition reactions, with the reaction rate varying depending on the type of reactant.

[0006] DGEBA can be induced to homopolymerize at room temperature by catalysts such as tertiary amines, substituted imidazoles, and amine complexes of Lewis acids such as BF3.

[0007] Aromatic glycidylamines (e.g., R 3 Structural formula II), in which the aromatic group is diphenylmethane, reacts similarly to glycidyl ethers, but due to its high functionality, it generates a highly cross-linked network.

[0008] Other oxirane-containing compounds react much more slowly with the same curing agents (e.g., amine-based curing agents) as described above, compared to aromatic glycidyl ethers or aromatic glycidylamines. For example, glycidyl ethers of aliphatic alcohols (R 1 Structural formula I) is a linear or branched aliphatic group and glycidyl esters (R) of fatty acids 2 Structural formula III) below, in which is a linear or branched aliphatic residue, reacts much more slowly at room temperature by addition with amines or homopolymerization compared to aromatic glycidyl ethers or aromatic glycidylamines (for example, curing in about twice, three times, four times, or even five times longer, depending on the specific curing agent used).

[0009] [ka] III

[0010] Curing time is a particularly important property in manufacturing applications where materials are used as adhesives. Room temperature curing can offer advantages over high-temperature curing, such as eliminating the need for additional firing steps, saving energy, reducing costs, enabling curing in the absence of a furnace, and avoiding damage to the substrate. While some room temperature curing adhesives are known, they generally do not offer rapid curing times. Longer curing times prolong the manufacturing process and create a risk that the bonded substrate may shift before it is fully cured. On the other hand, while some rapid curing adhesives (e.g., so-called "5-minute curing epoxy") are known, they are not typically used in manufacturing applications because they lack at least some desirable properties (e.g., peel resistance).

[0011] Oxirane-containing compounds of structural formulas I, II, and III are typically synthesized by the reaction of epichlorohydrin with molecules containing hydroxyl / carboxyl / amine groups (i.e., molecules with active hydrogen). However, epichlorohydrin, like other halogen-containing materials, is known to be a toxic substance associated with nasal and respiratory irritation and / or disease. Consequently, few companies handle epichlorohydrin, and therefore compounds derived from it can be expensive. The chemical industry still desires to reduce, and even eliminate, the health hazards that occur during synthesis, blending, and end use.

[0012] One alternative to the synthesis using epichlorohydrins is peracid epoxidation of carbon-carbon double bonds, which is relatively safer and easier to manufacture than using epichlorohydrins. However, products from peracid epoxidation are either completely unreactable (i.e., do not cure at all) or nearly unreactable (i.e., do not cure within 24 hours) compared to glycidyl ethers, glycidylamines, and glycidyl esters, whether aromatic or aliphatic. For example, aliphatic disubstituted oxirane rings (R 4 and R 5The following structural formula IV), where [the relevant group] is a linear or branched aliphatic group, does not react completely or almost completely with an amine addition reaction at room temperature.

[0013] [Chemical formula] IV

[0014] In recent years, concerns about renewability and sustainability in the environmental aspect have been increasing not only in the chemical industry. In this regard, bio-based and / or biorecyclable reactants are highly desirable. However, the use of this type of epoxy resin obtained by peracid epoxidation (e.g., in adhesives) is hindered by its complete non-reactivity or almost complete non-reactivity as described above.

[0015] A curing agent is needed that can cure an oxirane-containing material within about 2 hours at room temperature, more preferably within about 1 hour, more preferably within about 30 minutes, more preferably within about 20 minutes, more preferably within about 10 minutes, more preferably within about 5 minutes, and even more preferably within about 1 minute.

[0016] A curing agent is needed that can cure an oxirane-containing material at room temperature without carbonizing it (e.g., by heat due to exotherm).

[0017] An adhesive (e.g., a two-component composition) is needed that provides physical properties more preferable than those of conventional fast-curing adhesives.

[0018] An adhesive (e.g., a two-component composition) derived from an oxirane-containing material (e.g., an aliphatic disubstituted oxirane) produced by peracid epoxidation is needed, whereby epichlorohydrin can be excluded from its synthesis and thus the possibility of its presence as a residue in the final product can be excluded.

[0019] Adhesives (e.g., two-component compositions) derived from bio-based and / or bio-renewable reactants such as unsaturated natural oils are needed, which can provide a high composition ratio of bio-based raw materials.

Summary of the Invention

[0020] The present teachings provide a two-component composition (a two-component composition) for forming an adhesive that can address at least some of the needs identified above. The two-component composition may include a first part (first component) containing an aliphatic disubstituted oxirane and a second part (second component) containing an acidic phosphorus-based curing agent. The two-component composition may cure after mixing the first part and the second part with each other at a temperature of about 0°C to 50°C (e.g., room temperature (i.e., about 20°C to 25°C)). The two-component composition may cure within about 10 minutes, more preferably within about 5 minutes, and even more preferably within about 1 minute.

[0021] The aliphatic disubstituted oxirane may be derived from peracid epoxidation. The aliphatic disubstituted oxirane may be substituted with linear and / or branched groups. The aliphatic disubstituted oxirane may have a functionality greater than 2. The aliphatic disubstituted oxirane may be derived from (i) unsaturated natural oils, preferably polyunsaturated natural oils, and / or (ii) peracid epoxidation of elastomers.

[0022] The natural oil may include linseed oil and / or soybean oil.

[0023] The elastomer may include polybutadiene and / or natural rubber.

[0024] The acidic phosphorus-based curing agent may include an inorganic acid, an organic phosphorus-based compound, or a blend of both. The inorganic acid may include phosphoric acid, polyphosphoric acid, hypophosphorous acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof. The organic phosphorus-based compound may include alcohol-derived phosphate esters, aliphatic epoxy-derived phosphate esters, aromatic epoxy-derived phosphate esters, or any combination thereof.

[0025] Alcohol-derived phosphate esters, aliphatic epoxy-derived phosphate esters, and aromatic epoxy-derived phosphate esters may be monofunctional or polyfunctional, preferably polyfunctional. Both aliphatic disubstituted oxiranes and acidic phosphorus-based curing agents may be polyfunctional.

[0026] Alcohol-derived phosphate esters may be formed from the reaction of n-butanol with polyphosphate. Aliphatic epoxy-derived phosphate esters may be formed from the reaction of 2-ethylhexylglycidyl ether with phosphoric acid. Aromatic epoxy-derived phosphate esters may be formed from the reaction of phenylglycidyl ether with phosphoric acid. Although these phosphate esters were used in the examples shown, the range of phosphate esters that can be produced from alcohols and epoxy resins is broad, and there are few limitations on the types of phosphate esters that can be used according to the present invention.

[0027] The aliphatic disubstituted oxirane and the acidic phosphorus-based curing agent may be mixed in a stoichiometric ratio of about 1.5:1 to 1:1.5, more preferably about 1:1.

[0028] The two-part composition may also be thermosetting.

[0029] The two-part composition may further contain a foaming agent.

[0030] This instruction provides a two-part composition for forming an adhesive that can address at least some of the needs identified above. The two-part composition may comprise a first part containing an oxirane-containing compound and a second part containing an acidic phosphorus-based curing agent. The two-part composition may gel when the oxirane-containing compound and the acidic phosphorus-based curing agent are mixed at a temperature of about 0°C to 50°C (e.g., room temperature (i.e., about 20°C to 25°C)) (after the first and second parts are mixed together). The two-part composition may gel within about 10 minutes, more preferably within about 5 minutes, and even more preferably within about 1 minute.

[0031] 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 glycidylamine, a polyfunctional aliphatic glycidyl ether, a polyfunctional peracid epoxy, or any combination thereof.

[0032] 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 epoxyphenol 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 dimerized fatty acid. The polyfunctional aromatic glycidylamine may be a glycidylamine of methylenedianiline. The polyfunctional aliphatic glycidyl ether may be a glycidyl ether of castor oil. The polyfunctional peracid epoxy may be derived from the peracid epoxidation of unsaturated natural oils, preferably polyunsaturated natural oils, and / or elastomers.

[0033] The polyunsaturated natural oil may include linseed oil and / or soybean oil. The elastomer may include polybutadiene and / or natural rubber.

[0034] A polyfunctional peracid epoxy may have more than two functionalities.

[0035] The acidic phosphorus-based curing agent may contain an inorganic acid, an organophosphorus compound, or a blend of both.

[0036] Inorganic acids may include phosphoric acid, polyphosphate, subphosphoric acid, pyrophosphate, phosphonic acid, phosphinic acid, or any combination thereof. Organophosphorus compounds may include alcohol-derived phosphate esters, aliphatic epoxy-derived phosphate esters, aromatic epoxy-derived phosphate esters, or any combination thereof.

[0037] The organophosphorus compound may be monofunctional or polyfunctional, preferably polyfunctional. Both the oxirane-containing compound and the acidic phosphorus-based curing agent may be polyfunctional.

[0038] Alcohol-derived phosphate esters may be formed from the reaction of n-butanol with polyphosphate.

[0039] Aliphatic epoxy-derived phosphate esters may be formed by the reaction of 2-ethylhexylglycidyl ether with phosphoric acid. Aromatic epoxy-derived phosphate esters may be formed by the reaction of phenylglycidyl ether with phosphoric acid.

[0040] The oxirane-containing compound and the acidic phosphorus-based curing agent may be mixed in a stoichiometric ratio of about 1.5:1 to 1:1.5, more preferably in a stoichiometric ratio of about 1:1.

[0041] The two-part composition may be thermosetting.

[0042] The two-part composition may further contain a foaming agent. [Modes for carrying out the invention]

[0043] This teaching, through the improved two-part system described herein, satisfies one or more of the above needs. The descriptions and illustrations presented herein are intended to enable those skilled in the art to understand this teaching, its principles, and its practical applications. Those skilled in the art can adapt and apply this teaching in various forms to best suit the requirements of a particular application. Accordingly, the detailed embodiments of this teaching described herein are not intended to be exhaustive or restrictive. Accordingly, the scope of this teaching should not be determined by reference to the following description, but rather by reference to the scope of the appended claims and together with the entire scope of equivalents that such claims have. All disclosures of documents and references, including patent applications and publications, are incorporated herein by reference for all purposes. Other combinations are also possible, as can be read from the following claims, and these claims are also incorporated herein by reference.

[0044] This instruction provides a two-part composition comprising one or more oxirane-containing compounds that cures at a temperature of about 0°C to 50°C (for example, at room temperature (i.e., about 20°C to 25°C)).

[0045] This instruction is particularly applicable to oxirane-containing compounds that do not react or substantially react with conventional amine-based curing agents at room temperature. For example, it is known that at room temperature, aliphatic disubstituted oxiranes do not react at all (i.e., do not cure at all) or do not react almost completely (i.e., do not cure within 24 hours) with conventional curing agents such as amines.

[0046] This instruction can be further applied to oxirane-containing compounds that react slowly at room temperature. For example, glycidyl ethers of aliphatic alcohols and glycidyl esters of fatty acids may cure with conventional amine-based curing agents in about 6 hours or more, 10 hours or more, 14 hours or more, or even 18 hours or more, making them impractical for many applications.

[0047] This instruction may be further applicable to oxirane-containing compounds that react rapidly at room temperature. For example, while aromatic glycidyl ethers can be cured in 5 hours or less, 4 hours or less, 3 hours or less, or even 2 hours or less with conventional amine-based curing agents, the curing agent in this instruction may result in curing in minutes rather than hours.

[0048] The adhesives described herein may achieve room temperature curing in less than 24 hours. Curing times 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. The term "rapid" as used herein may encompass any of these aforementioned curing times.

[0049] The curing time of the adhesive may be suitable for high-throughput manufacturing processes (e.g., automotive manufacturing), eliminating the need to extend assembly fixture time to allow the adhesive to cure. Furthermore, the adhesives described herein may be formulated to foam (i.e., expand in volume). Therefore, the rapid curing time of the adhesive can be advantageous in foaming applications, as the adhesive cures before volume loss and / or dripping of trapped air may occur.

[0050] As used herein, curing may mean a polymerization reaction of linear extension and / or crosslinking, resulting in a cured material that increases in viscosity, hardens, solidifies, or a combination thereof. Curing may also be referred to herein as gelation.

[0051] As used herein, foaming may mean that gas is generated within the material (e.g., via a blowing agent, or other substance called a leavening agent) and the material expands (e.g., a volume expansion of approximately 50% to 2,000%). The polymer matrix may trap the gas within it. The curing of the material may occur in conjunction with foaming, and the volume expansion may be fixed by curing. In this regard, the activation of curing and foaming may be selected to occur in conjunction. Curing and foaming may occur at different times or substantially simultaneously.

[0052] This instruction aims for relatively fast curing time, foaming time, or both, compared to other curing agents or curing agent systems that function without the application of stimuli (e.g., heat).

[0053] Foaming, if present, may begin before the complete curing of the resulting reaction product. The foaming time of the reaction product (i.e., the time frame during which the adhesive actively foams) may be 30 minutes or less, 20 minutes or less, or even 10 minutes or less. The foaming time of the reaction product may also be approximately 1 minute or more, or even 5 minutes or more.

[0054] The adhesive can cure at temperatures of approximately 0°C to 50°C. Curing of the adhesive can be activated at room temperature. If desired, volume expansion may be increased by raising the temperature of the adhesive during mixing and / or the temperatures of the first and / or second parts of the two-part composition.

[0055] The adhesives of this instruction may be two-part compositions, where the first part is mixed with the second part, usually at the time of application to the substrate. The reaction products referred to herein may be completely cured (i.e., without further crosslinking). Curing may begin at or after the mixing of the first and second parts. Curing may begin approximately immediately after the mixing of the first and second parts. Curing may be delayed for a certain period of time after the mixing of the first and second parts.

[0056] Room-temperature curing of the oxirane-containing compound may be achieved by reaction with one or more acidic phosphorus-based curing agents. The first part may contain one or more oxirane-containing compounds, and the second part may contain one or more acidic phosphorus-based curing agents. Furthermore, each part of the two-part composition may contain one or more additives for modifying the properties of the adhesive.

[0057] Curing may result from a chemical reaction between the oxirane-containing compound and the acidic phosphorus-based curing agent. Therefore, curing may be initiated by mixing the first and second parts. The acidic phosphorus-based curing agent of this teaching may react to crosslink the oxirane-containing compound, to extend the chain of the oxirane-containing compound, or both.

[0058] The adhesive may be thermoplastic or thermosetting. Thermosetting may be characterized by a crosslinking network. The degree of crosslinking may be controlled by adjusting the functionalities of the oxirane-containing compound, the acidic phosphorus-based curing agent, or both. In this teaching, it is intended that if metal carbonates are included in the composition, they may affect the degree of crosslinking by neutralizing part of the acidic component of the second part. Thermosetting may be achieved by selecting an oxirane-containing compound, an acidic phosphorus-based curing agent, or both having more than two functionalities. Preferably, the adhesive may be thermosetting.

[0059] The properties of the adhesive (e.g., peel resistance) may be controlled by the presence of one or more copolymers present with the oxirane-containing compound, the selection of desirable functional groups in the oxirane-containing compound, the presence of one or more additives, or any combination thereof.

[0060] Oxirane-containing compounds (e.g., aliphatic disubstituted oxiranes) may be formed by peracid epoxidation. In this regard, the process for forming aliphatic disubstituted oxiranes may be epichlorohydrin-free or substantially epichlorohydrin-free, and the final product may not contain epichlorohydrin residue. This teaching is intended to show that compositions may contain oxirane-containing compounds derived from peracid epoxidation and oxirane-containing compounds derived from epichlorohydrin.

[0061] Oxirane-containing compounds (e.g., aliphatic disubstituted oxiranes) and / or acidic phosphorus-based curing agents may be derived from bio-based and / or bio-renewable resources. For example, aliphatic disubstituted oxiranes may be derived from natural oils.

[0062] Oxirane-containing compounds. The oxirane-containing compounds listed below are illustrative and useful for teaching embodiments of the present invention. They are not intended to limit the scope of the invention. It will become clear that the teachings of the present invention are applicable to a wide range of oxirane compounds and acidic phosphorus-based curing agents.

[0063] The adhesive may contain one or more oxirane-containing compounds. While several additional advantages may be attributed to the aliphatic disubstituted oxiranes described herein, faster curing times can be achieved with a wide range of oxirane-containing compounds compared to conventional amine-based curing agents.

[0064] The polymer network formed by the oxirane-containing compound can provide structural and physical properties to the adhesive. Additional properties may be imparted to the adhesive by including one or more copolymers, additives, or both. If the adhesive foams, the polymer network formed by the oxirane-containing compound may trap gas within it.

[0065] 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 glycidylamine, a polyfunctional aliphatic glycidyl ether, an aliphatic disubstituted oxiran, or any combination thereof.

[0066] The adhesive may contain one or more bifunctional aromatic glycidyl ethers. The glycidyl ether is defined as structural formula I in this specification.

[0067] [ka] I (In the formula, R 1 It may also be characterized by containing an aromatic group but not an additional oxirane.

[0068] The bifunctional aromatic glycidyl ether may have an epoxy equivalent of approximately 140 g / eq or more, 150 g / eq or more, or even 160 g / eq or more (measured according to ASTM D1652-11). The bifunctional aromatic glycidyl ether may have an epoxy equivalent of approximately 200 g / eq or less, 190 g / eq or less, 180 g / eq or less, or even 170 g / eq or less (measured according to ASTM D1652-11).

[0069] The bifunctional aromatic glycidyl ether may have a viscosity of approximately 1,500 cPs (1,500 mPa·s) or more, 2,000 cPs (2,000 mPa·s) or more, 2,500 cPs (2,500 mPa·s) or more, or even 3,000 cPs (3,000 mPa·s) or more at room temperature (measured according to ASTM D2393-86). The bifunctional aromatic glycidyl ether may have a viscosity of approximately 5,500 cPs (5,500 mPa·s) or less, 5,000 cPs (5,000 mPa·s) or less, 4,500 cPs (4,500 mPa·s) or less, 4,000 cPs (4,000 mPa·s) or less, or even 3,500 cPs (3,500 mPa·s) or less (measured according to ASTM D2393-86) at room temperature.

[0070] The bifunctional aromatic glycidyl ether may contain a bisphenol F epoxy resin. An example of a bisphenol F epoxy resin is Epokukdo YDF-170, which is commercially available from Kukdo Chemical Co., Ltd.

[0071] The bifunctional aromatic glycidyl ether may contain a bisphenol A epoxy resin. An example of a bisphenol A epoxy resin is Epokukdo YD-128, which is commercially available from Kukdo Chemical Co., Ltd.

[0072] The adhesive may contain one or more polyfunctional aromatic glycidyl ethers. The polyfunctional aromatic glycidyl ether may be characterized by structural formula I herein, where R 1 It contains an aromatic group and an additional oxirane. The polyfunctional aromatic glycidyl ether may have a functionality of about 2.3 to 3.0 (e.g., 2.6).

[0073] The polyfunctional aromatic glycidyl ether may have an epoxy equivalent (measured in accordance with ASTM D1652-11) of about 150 g / eq or more, 155 g / eq or more, 160 g / eq or more, or even 165 g / eq or more. The polyfunctional aromatic glycidyl ether may have an epoxy equivalent (measured in accordance with ASTM D1652-11) of about 185 g / eq or less, 180 g / eq or less, 175 g / eq or less, or even 170 g / eq or less.

[0074] The polyfunctional aromatic glycidyl ether may have a viscosity (measured in accordance with ASTM D2393-86) of about 16,000 cPs (16,000 mPa·s) or more, 17,000 cPs (17,000 mPa·s) or more, 18,000 cPs (18,000 mPa·s) or more, 19,000 cPs (19,000 mPa·s) or more, or even 20,000 cPs (20,000 mPa·s) or more at room temperature. The polyfunctional aromatic glycidyl ether may have a viscosity (measured in accordance with ASTM D2393-86) of about 25,000 cPs (25,000 mPa·s) or less, 24,000 cPs (24,000 mPa·s) or less, 23,000 cPs (23,000 mPa·s) or less, 22,000 cPs (22,000 mPa·s) or less, or even 21,000 cPs (21,000 mPa·s) or less at room temperature.

[0075] The polyfunctional aromatic glycidyl ether may include an epoxy phenolic novolak resin. Exemplary epoxy phenolic novolak resins may include DEN (registered trademark) 426 commercially available from Olin Corporation.

[0076] The adhesive may include one or more difunctional aliphatic glycidyl ethers. The difunctional aliphatic glycidyl ether may be characterized by Structural Formula I herein, where R 1 is aliphatic and does not contain additional oxiranes.

[0077] The bifunctional aliphatic glycidyl ether may have an epoxy equivalent of approximately 110 g / eq or more, 115 g / eq or more, 120 g / eq or more, or even 125 g / eq or more (measured according to ASTM D1652-11). The bifunctional aliphatic glycidyl ether may have an epoxy equivalent of approximately 150 g / eq or less, 145 g / eq or less, 140 g / eq or less, or even 135 g / eq or less (measured according to ASTM D1652-11).

[0078] The bifunctional aliphatic glycidyl ether may include the diglycidyl ether of butanediol. An example of the diglycidyl ether of butanediol may be KF Epiol DE200, which is commercially available from Kukdo Chemical.

[0079] The adhesive may contain one or more difunctional aliphatic diglycidyl esters. The difunctional aliphatic diglycidyl ester may be characterized by structural formula III herein, where R 2 It is aliphatic and does not contain additional oxirane.

[0080] The bifunctional aliphatic glycidyl ester may have an epoxy equivalent of approximately 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 (measured according to ASTM D1652-11). The bifunctional aliphatic diglycidyl ester may have an epoxy equivalent of approximately 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 (measured according to ASTM D1652-11).

[0081] Difunctional aliphatic glycidyl esters may have a viscosity of approximately 300 cPs (300 mPa·s) or more, 400 cPs (400 mPa·s) or more, or even 500 cPs (500 mPa·s) or more (measured according to ASTM D2393-86) at room temperature. Difunctional aliphatic diglycidyl esters may have a viscosity of approximately 1,000 cPs (1,000 mPa·s) or less, 900 cPs (900 mPa·s) or less, 800 cPs (800 mPa·s) or less, or even 700 cPs (700 mPa·s) or less (measured according to ASTM D2393-86) at room temperature.

[0082] The difunctional aliphatic diglycidyl ester may include diglycidyl esters of dimerized fatty acids. An example of a diglycidyl ester of a dimerized fatty acid may be Epokukdo YD-171, which is commercially available from Kukdo Chemical.

[0083] The adhesive may contain one or more polyfunctional aromatic glycidylamines. The polyfunctional aromatic glycidylamine may be characterized by structural formula II, where R 3 It contains an aromatic group.

[0084] Polyfunctional aromatic glycidylamines may have an epoxy equivalent of approximately 100 g / eq or more, 105 g / eq or more, or even 110 g / eq or more (measured according to ASTM D1652-11). Polyfunctional aromatic glycidylamines may have an epoxy equivalent of approximately 130 g / eq or less, 125 g / eq or less, or even 120 g / eq or less (measured according to ASTM D1652-11).

[0085] Polyfunctional aromatic glycidylamines may have viscosities of approximately 2,500 cPs (2,500 mPa·s) or more, 3,000 cPs (3,000 mPa·s) or more, 3,500 cPs (3,500 mPa·s) or more, or even 4,000 cPs (4,000 mPa·s) or more at 50°C (measured according to ASTM D2393-86). Polyfunctional aromatic glycidylamines may have viscosities of approximately 7,000 cPs (7,000 mPa·s) or less, 6,500 cPs (6,500 mPa·s) or less, 6,000 cPs (6,000 mPa·s) or less, 5,500 cPs (5,500 mPa·s) or less, or even 5,000 cPs (5,000 mPa·s) or less (measured according to ASTM D2393-86) at 50°C.

[0086] The polyfunctional aromatic glycidylamine may include a methylenedianiline glycidylamine. An example of a methylenedianiline glycidylamine is Epotec® YDM-441, which is commercially available from Azelis.

[0087] The adhesive may contain one or more polyfunctional aliphatic glycidyl ethers. The polyfunctional aliphatic glycidyl ether may be characterized by structural formula I, where R 1 It is aliphatic and can be epoxidized at multiple sites.

[0088] The polyfunctional aliphatic glycidyl ether may have an epoxy equivalent of approximately 450 g / eq or more, 500 g / eq or more, or even 550 g / eq or more (measured according to ASTM D1652-11). The polyfunctional aliphatic glycidyl ether may have an epoxy equivalent of approximately 700 g / eq or less, 650 g / eq or less, or even 600 g / eq or less (measured according to ASTM D1652-11).

[0089] The polyfunctional aliphatic glycidyl ether may include castor oil glycidyl ether. An example of a castor oil polyfunctional glycidyl ether is Kukdo PE-412, which is commercially available from Kukdo Chemical. The polyfunctional aliphatic glycidyl ether may also include glycerol triglycidyl ether. An example of a glycerol triglycidyl ether is Erysis® GE-38, which is available from Huntsman.

[0090] The adhesive may contain one or more polyfunctional peroxy epoxidants. Polyfunctional peroxy epoxidants may be advantageous in terms of low cost, wide availability, simple manufacturing methods, and applicability of peroxy epoxidation to a wide range of organic compounds having unsaturated carbon-carbon double bonds.

[0091] The polyfunctional peracid epoxy may contain an aliphatic disubstituted oxiranes. The aliphatic disubstituted oxiranes may be derived from peracid epoxidation. The aliphatic disubstituted oxiranes may be substituted with linear and / or branched groups. The aliphatic disubstituted oxiranes may include those conforming to structural formula IV herein, where R 4 and R 5 R is a linear and / or branched aliphatic group that also contains an oxirane ring. It is also conceivable that one or more oxirane rings on a polyfunctional peracid epoxide may be located at the terminal end of the compound, in which case R 4 or R 5is a H atom. An exemplary oxirane compound of this type is 1,7-octadiene diepoxide. The terminal epoxide group can be expected to be slightly more reactive than the bisubstituted group. Another special class of peracid epoxides is cycloaliphatic epoxides, in which the oxirane ring is formed on a cyclohexene ring, resulting in a bicyclic compound with further ring strain on the oxirane ring. An exemplary compound of this type is (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), available as Syna21 from Synasia, Inc. Due to the ring strain, these compounds react with conventional amine curing agents, but the reaction is slow. However, they react rapidly with the acidic phosphorus curing agents of the disclosed invention.

[0092] Aliphatic disubstituted oxiranes may contain two or more oxiran groups (i.e., two or more functionalities). In this regard, with at least two functionalities, an extended polymer chain may be formed, and with more than two functionalities, crosslinking may be achieved.

[0093] Aliphatic disubstituted oxiranes may be derived from the peracid epoxidation of unsaturated natural oils and / or elastomers. Preferably, the natural oil is a polyunsaturated natural oil, but this teaching intends any suitable polyunsaturated natural oil to be subjected to peracid epoxidation.

[0094] Examples of natural oils include linseed oil, soybean oil, cashew nut shell liquid ("CNSL"), tall oil, or any combination thereof. Peracid epoxidation of linseed oil produces "epoxidized linseed oil" ("ELO"). Peracid epoxidation of soybean oil produces "epoxidized soybean oil" ("ESO"). Peracid epoxidation of cashew nut shell liquid produces "epoxidized cashew nut shell liquid" ("ECNSL").

[0095] The natural oil may be monounsaturated (e.g., tall oil and CNSL) or polyunsaturated (e.g., linseed oil and soybean oil), with each unsaturated moiety providing epoxy group moieties. For greater crosslinking, the natural oil is preferably polyunsaturated. This teaching assumes the use of blends of monounsaturated and polyunsaturated natural oils. Monounsaturated natural oils may function as reactive plasticizers, even if they do not provide crosslinking.

[0096] Epoxy-modified natural oils may be bio-based and / or bio-renewable; that is, natural oils may be extracted from natural resources.

[0097] Epoxidized natural oils have traditionally been used as stabilizers for chlorinated polymers (e.g., polyvinyl chloride). However, their conventional use in adhesives has been limited, due to their potentially slow or no reactivity with conventional epoxy curing agents, including amine-based curing agents, which constitute the largest group of room-temperature epoxy curing agents. While not intended to be theoretically bound, this reactivity may be due to the incompatibility between the hydrophobic epoxidized natural oils and the polar nitrogen groups in such curing agents. However, the peracid epoxidation products discussed herein (see, e.g., Structure IV) may not have adjacent heteroatoms.

[0098] The polyfunctional peracid epoxy may also include peracid epoxidized liquid, semi-solid, or solid unsaturated elastomers. The elastomer may include a liquid elastomer and / or a solid or semi-solid elastomer with a lower molecular weight. The liquid elastomer may be liquid at room temperature and may be flowable. The solid or semi-solid elastomer may be solid at room temperature and not flowable, or it may exhibit viscoelasticity at room temperature. The elastomer may impart flexibility to the curing adhesive.

[0099] The peracid epoxidized elastomer may contain polybutadiene and / or natural rubber. The peracid epoxidized polybutadiene may be liquid, semi-solid, or solid. Polybutadiene may be advantageous in providing high density of oxirane groups through peracid epoxidation.

[0100] Aliphatic disubstituted oxiranes may have a room temperature viscosity (measured according to ASTM D2393-86) of approximately 600 cPs (600 mPa·s) or more, 650 cPs (650 mPa·s) or more, or even 700 cPs (700 mPa·s) or more. Aliphatic disubstituted oxiranes may have a room temperature viscosity (measured according to ASTM D2393-86) of approximately 900 cPs (900 mPa·s) or less, 950 cPs (950 mPa·s) or less, 800 cPs (800 mPa·s) or less, or 750 cPs (750 mPa·s) or less.

[0101] Aliphatic disubstituted oxiranes may have an oxiran oxygen content of approximately 6% by weight or more, 7% by weight or more, or even 8% by weight or more. Aliphatic disubstituted oxiranes may have an oxiran oxygen content of approximately 11% by weight or less, 10% by weight or less, or even 9% by weight or less.

[0102] An example of an aliphatic disubstituted oxiran may be Epoxol® 9-5 (bio-based high-oxiran epoxidized linseed oil), which is commercially available from ACS Technical Products.

[0103] Acidic phosphorus-based hardening agent. The adhesive may contain one or more acidic phosphorus curing agents. The acidic phosphorus curing agents may provide commercially useful curing times. The acidic phosphorus curing agents may provide a curing time 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, and even more preferably about 1 minute or less for the adhesive.

[0104] The acidic phosphorus-based curing agent described herein may react with oxirane-containing compounds that do not react at all or substantially with conventional alkaline epoxy curing agents based on amine hydrogen or amine-derived curing agents based on nitrogen.

[0105] The acidic phosphorus curing agent described herein may react faster than the alkaline epoxy curing agent with many oxirane-containing compounds that react with amine hydrogen-based alkaline epoxy curing agents or nitrogen-based curing agents (e.g., oxirane-containing compounds including glycidyl ethers, glycidyl esters, and glycidylamines, whether aromatic or aliphatic).

[0106] The acidic phosphorus-based curing agent may provide crosslinking, homopolymerization, or both.

[0107] The acidic phosphorus-based curing agent may contain phosphorus oxide and may contain an acidic hydroxyl group. The acidic hydroxyl group may be ionizable in the presence of moisture. The acidic phosphorus-based curing agent may contain at least one ionizable -POH group as shown below.

[0108] [ka]

[0109] To effectively form a three-dimensional crosslinking network, it is preferable that the acidic phosphorus curing agent has an average functionality greater than 2. This can be achieved by using a blend of acidic phosphorus curing agents. For example, blending a monophosphate ester of phosphoric acid containing two ionizable -POH groups with phosphoric acid yields a curing agent mixture with an average functionality between 2 and 3, depending on the ratio used. Alternatively, blending a bifunctional or even monofunctional acidic phosphorus curing agent with a polyfunctional acidic phosphorus curing agent may yield a curing agent with an average functionality greater than 2.

[0110] By reacting alcohols with two, three, or more functionalities with P2O5 or polyphosphate, acidic phosphorus-based curing agents with high functionalities of three, four, five, or more can be obtained. Similarly, by reacting epoxides with two, three, or more functionalities with phosphoric acid, acidic phosphorus-based compounds with a higher number of acidic-POH groups can be obtained.

[0111] The acidic phosphorus curing agent may contain an inorganic acid, an organophosphorus compound, or both.

[0112] The inorganic acid may include phosphoric acid (H3PO4), polyphosphate, subphosphate (H4P2O6), pyrophosphate (H4P2O7), phosphonic acid (H2PO3), phosphinic acid (H3PO2), or any combination thereof.

[0113] The organophosphorus compounds may include alkyl and aryl esters of phosphoric acid, alkyl or aryl phosphonates, dialkyl or diaryl phosphinates, or any combination thereof.

[0114] Preferred organophosphorus compounds may include esters of phosphoric acid. Compared to other acidic phosphorus compounds, esters of phosphoric acid are generally less expensive and easier to synthesize.

[0115] The organophosphorus compounds may be selected from the mono-esters or di-esters shown below.

[0116] [ka]

[0117] This instruction assumes that the composition may contain triesters, as described above. Although they are usually unreactive, triester residues may be present as reaction byproducts in the synthesis of organophosphorus compounds or added as mixtures with monoesters and / or diesters.

[0118] Organophosphorus compounds may also be obtained from the reaction of an epoxy group with phosphoric acid, as shown below.

[0119] [ka]

[0120] Substitution (e.g., to form esters) can reduce the functionality of the curing agent and may lead to a decrease in crosslinking density, thus potentially resulting in a decrease in elastic modulus, an increase in fracture strain, a decrease in glass transition temperature, an increase in fracture energy, or a combination thereof. Substitution may also introduce parts to impart other desirable properties to the cured composition.

[0121] Substituted organophosphorus compounds (e.g., monoesters of phosphoric acid) may be desirable for crosslinking reactions, either alone or in blends with inorganic acids. In this regard, inorganic acids exhibit rapid reaction rates and may result in excessive exothermic energy release, which could lead to carbonization of the adhesive. Therefore, blending with substituted organophosphorus compounds may mitigate the excessive exothermic energy release that may occur when using inorganic acids alone.

[0122] Phosphoric acid esters may be produced by the reaction of an alcohol with phosphorus pentoxide (P2O5), polyphosphate, or orthophosphate. Phosphoric acid esters may have a high proportion of monoester and a low free phosphoric acid content. Phosphoric acid esters may also have an excess of free phosphoric acid. Phosphoric acid esters may be synthesized to provide a free phosphoric acid content, or they may be included in blends with phosphoric acid.

[0123] Examples of organophosphorus compounds may include those characterized by the following structural formulas V, VI, and VII.

[0124] The following structural formula V shows a monobutyl phosphate ester formed by the reaction of n-butanol with a slightly stoichiometrically excess amount of polyphosphate.

[0125] [ka] V

[0126] Phosphate esters can also be synthesized by the reaction of epoxy with excess phosphoric acid, as described in U.S. Patent No. 10,550,220 B2, which is incorporated herein by reference in whole for all purposes. For example, structure VI below is formed by the reaction of 2-ethylhexylglycidyl ether with a slightly excess of 85% phosphoric acid.

[0127] [ka] VI

[0128] Similarly, structure VII is formed by the reaction of phenylglycidyl ether with a slightly excess of 85% phosphate.

[0129] [ka] VII

[0130] Foaming may be achieved by the presence of one or more metal carbonates, leavening agents, or both in the adhesive. Metal carbonates (e.g., calcium carbonate) may be preferred because they are reactive with the acidic phosphorus curing agents of this teaching. This teaching intends leavening agents such as physical leavening agents and / or chemical leavening agents. Physical leavening agents and / or chemical leavening agents may be present together with metal carbonates.

[0131] Suitable chemical leavening agents may include dinitrosopentamethylenetetraamine, azodicarbonamide, dinitroso-pentamethylenetetraamine, 4,4'-oxy-bis-(benzene-sulfonylhydrazide), trihydrazinotriadin, N,N'-dimethyl-N,N'-dinitroso-terephthalamide, or any combination thereof.

[0132] A suitable example of a physical expansion agent may be the one sold by Akzo Nobel under the trademark name ExpanseL®.

[0133] Suitable examples of metal carbonates may include Hubercarb® Q2, Q4, Q200, or Q325 calcium carbonate from Huber Engineered Materials.

[0134] Metal carbonates, leavening agents, or both may be present in amounts of approximately 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, or further 2% by weight or less. If metal carbonates are used, they may be present on the first side because they are reactive with the second side. Leavening agents may be present on the first side and / or the second side.

[0135] The adhesive may contain one or more functional additives to improve one or more different properties of the composition. Examples of suitable functional additives include tougheners (e.g., core-shell polymer particles), reinforcing fibers, antioxidants, ozone inhibitors, UV absorbers, thixotropic agents, antistatic agents, colorants, coupling agents, curing agents, flame retardants, minerals, swelling agents, heat stabilizers, impact modifiers, lubricants, plasticizers, preservatives, processing aids, stabilizers, and any combination thereof. The additives may be present in the first and / or second parts of the adhesive.

[0136] [Example] The materials used in the following examples are listed in Table 1. These include oxirane-containing compounds as described herein, which include both those derived from epichlorohydrins to form glycidyl ethers, amines, and esters, and those derived from the peracid epoxidation of carbon-carbon double bonds. Table 1 also lists conventional amine-based curing agents and acid-phosphorus-based curing agents.

[0137] [Table 1]

[0138] Table 2 below shows the gelation times (in minutes) for various oxirane-containing compounds in reactions with both conventional amine curing agents (e.g., aliphatic amines, alicyclic amines, tertiary amines, polyamides, and amide amines) and acidic phosphorus-based curing agents according to this instruction.

[0139] Sample preparation. Samples were prepared by mixing oxirane groups with amine hydrogen groups (-NH) or acidic phosphorus groups (-POH) in a 1:1 stoichiometric ratio, such that the combined mass of the oxirane-containing compound and the curing agent was 30 grams. Tertiary amines are an exception, as they do not contain either reactive amine hydrogen groups or acidic phosphorus groups. In this case, each oxirane-containing compound was mixed with a tertiary amine in a ratio of 3.1 equivalents of oxirane groups to 1 equivalent of tertiary amine groups (for example, when mixing a tertiary amine with a liquid bisphenol A epoxy resin having 190 grams of epoxy equivalent ("EEW") per equivalent, this corresponds to a mixing ratio of 15 phr (parts per 100 parts of resin)).

[0140] Test procedure. The gelation time was measured using a Hot Pot Gel Timer (Catalog No. 11576, commercially available from Gardco). The first and second portions were each filled into separate containers and mixed at room temperature using a high-speed mixer at 2450 RPM for 30 seconds. The total volume of the first and second portions was 30 g. This 30 g mixture was then placed in the Hot Pot Gel Timer and tested at room temperature without using a heating element. The gelation time was measured from the moment the first and second portions were mixed. Finally, the gelation time was determined when the rotating hook driven by the Gel Timer stopped due to the fluid viscosity of the sample.

[0141] For samples that hardened in less than 30 seconds using the method described above, the first and second parts were mixed manually, and the gelation time was determined when the mixing device stopped due to the fluid viscosity of the sample during manual mixing.

[0142] [Table 2]

[0143] Aromatic glycidyl ethers (glycidyl ether of bisphenol F and epoxyphenol novolac resins) showed the fastest curing time compared to conventional amine curing agents, and even faster curing time with the acidic phosphorus-based curing agent described in this teaching. This indicates that acidic phosphorus-based compounds are suitable for use in rapid curing systems.

[0144] Similar observations were made with glycidylamine (glycidylamine of methylenedianiline). Although curing is slower than aromatic glycidyl ethers, glycidylamine, which takes several hours to cure with conventional anine curing agents, cures in just a few minutes when using an acidic phosphorus-based curing agent.

[0145] Difunctional aliphatic glycidyl ethers and glycidyl esters cured more slowly with conventional amine curing agents than those mentioned above; in the case of amidoamines, curing did not occur within 1440 minutes (24 hours). Gelation times exceeding 24 hours make this system impractical for use in many adhesive applications. However, these epoxy resins, in most cases, gelled within minutes with the acidic phosphorus compounds described herein. The aliphatic epoxy-derived phosphate esters were an exception, as they did not gel the difunctional aliphatic glycidyl ethers within 24 hours. This epoxy resin-curing agent combination generated significant heat, suggesting that a reaction had occurred. The final viscosity of the reacted system was lower than the initial viscosity of the mixture, suggesting that the curing reaction involved side reactions, possibly hydrolysis, which hindered the formation of a three-dimensional bonding network and inhibited gelation.

[0146] The polyfunctional aliphatic glycidyl ether selected for evaluation was epoxidized castor oil. This was chosen due to its high biorenewable carbon content. Contrary to expectations, this epoxidized castor oil did not gel within 24 hours with conventional curing agents. While not intended to be bound by theory, this is thought to be due to the low density of reaction sites because the selected polyfunctional aliphatic glycidyl ether has a high epoxy equivalent (EEW). Furthermore, the aliphatic nature of epoxidized castor oil may have reduced its compatibility with amine curing agents, contributing to the delayed gelation. However, this slow-gelling glycidyl ether gelled within a few hours when using the acidic phosphorus-based curing agent of this teaching. This gelation time is sufficiently rapid for use in many thermosetting adhesive applications. Another polyfunctional glycidyl ether selected for demonstration of the present invention was triglycidyl ether of glycerol. This triglycidyl ether has a lower epoxy equivalent, and therefore can generate a higher crosslink density in a shorter time, resulting in a shorter gelation time.

[0147] It is important to note that even with amine-acidified mercaptan curing systems used in many standard fast-curing epoxy systems, peracid epoxys do not gel within 1440 minutes. However, acidic phosphorus compounds can rapidly gel peracid epoxys.

[0148] Peracid epoxy, in this case epoxidized linseed oil, is relatively unresponsive to conventional amine curing agents and fast-curing mercaptan curing systems, but it has been demonstrated in Table 2 that it gels within 1 minute when cured with the acidic phosphorus-based curing agent described in this teaching. While not intended to be theoretically bound, this rapid gelation is thought to be due to the combination of the higher functionality of epoxidized linseed oil and the inherently more reactive acidic-POH groups of the curing agent used.

[0149] Other strongly acidic inorganic acids can induce polymerization of epoxy resins, including resins produced by peracid epoxidation. For example, 96% sulfuric acid and 70% nitric acid can induce polymerization. However, it should be noted that the reaction is often extremely rapid and exothermic, and even small amounts can result in carbonization. Since monoacidic nitric acid should not normally induce the formation of a three-dimensional network, reactions with monofunctional inorganic acids such as nitric acid also suggest that some degree of homopolymerization occurs in the acid-cured epoxy system. This teaching intends to include nitric acid to induce homopolymerization of resins produced by peracid epoxidation.

[0150] The use of phosphoric acid is preferred, and by using a monoester of phosphoric acid alone or in combination with phosphoric acid as a curing agent, a means is provided to form a three-dimensional thermosetting material that allows both chain extension and crosslinking of the epoxy resin while mitigating and controlling the reactivity.

[0151] It should be understood that the above description is illustrative and not intended to be limiting. Therefore, the detailed embodiments of the invention described herein are not intended to be exhaustive or limiting. Those skilled in the art will see many embodiments and applications beyond those provided.

[0152] Therefore, the scope of the invention should not be determined by reference to the above description, but by reference to the scope of the appended claims and by considering the entire scope of equivalents that such claims have. In the following claims, the omission of any aspect of the subject matter disclosed herein shall not be construed as a abandonment of that subject matter, nor as a failure of the inventor to consider that subject matter to be part of the disclosed subject matter of the invention.

[0153] Multiple elements may be provided by a single, unified element, or a single element may be split into multiple distinct elements. The disclosure of "a" or "one" when describing an element is not intended to exclude additional elements.

[0154] In this specification, terms such as "first," "second," and "third" may be used to describe various components, but these components are not limited by these terms. These terms may be used to distinguish one component from another. In this specification, terms such as "first," "second," and other numerical terms do not imply order or sequence unless clearly indicated by the context. Therefore, the first component described herein may be referred to as the second component without deviation from this instruction.

[0155] When describing measurements, percentages, or ratios, the terms “generally,” “substantially,” or “approximately” may mean within ±10%, ±5%, or even ±1%. When describing measurements, percentages, or ratios, the terms “generally,” “substantially,” or “approximately” may mean within ±0.01%, ±0.1%, or even ±0.5%.

[0156] Unless otherwise specified, all ranges include both endpoints and all numerical values ​​between those endpoints. The use of "approximately" or "about" in relation to a range applies to both ends of that range. Therefore, "approximately 20-30" is intended to include "approximately 20-approximately 30," including at least the specified endpoint.

[0157] As used herein, “aliphatic” preferably means a linear or branched hydrocarbon group containing up to 24 carbon atoms, wherein the bond between any two carbon atoms is a single, double, or triple bond. The aliphatic group preferably contains 1 to about 24 carbon atoms, more typically 1 to about 12 carbon atoms, and even more preferably 1 to about 6 carbon atoms.

[0158] As used herein, "alicyclic" preferably means a saturated or unsaturated non-aromatic hydrocarbon moiety having 1 to 3 rings, each ring having 3 to 8 (preferably 3 to 6) carbon atoms.

[0159] As used herein, "aromatic" preferably means a monocyclic or polycyclic carbocyclic group having one or more aromatic rings. Examples of aryl groups include, but are not limited to, phenyl and naphthyl groups.

[0160] Unless otherwise specified, any numerical values ​​described herein include all values ​​from the lower limit to the upper limit in increments of one unit, provided that there is at least a difference of two units between any lower limit and any upper limit. For example, if a value for the quantity, property, or process variable of an ingredient, such as temperature, pressure, or time, is described as, for example, 1 to 90, 20 to 80, or 30 to 70, then intermediate range values ​​(e.g., 15 to 85, 22 to 68, 43 to 51, etc.) are intended to be included in the teachings herein. Similarly, individual intermediate values ​​are also included in the teachings herein. For values ​​less than 1, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 as appropriate. These are merely examples of what is intended in detail, and all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to be expressly described in a similar manner in this application. Unless otherwise specified, all ranges include both endpoints and all numerical values ​​between those endpoints.

[0161] As can be seen, the teaching of quantities expressed in “parts by weight” in this specification is also intended to be expressed in weight percentages for the same range. Therefore, the expression of a range in the form of “at least x parts by weight of the resulting composition” is also intended to be the teaching of the same range of quantities as “x weight percent of the resulting composition.”

[0162] When describing a combination, the term "consisting essentially of" includes any other such elements, materials, components, or processes that do not substantially affect the basic and novel properties of the identified elements, materials, components, or processes of the combination. In this specification, the use of the terms "comprising" or "including" when describing a combination of elements, materials, components, or processes also implies embodiments that are essentially composed of those elements, materials, components, or processes.

[0163] All disclosures in the literature and references, including patent applications and publications, are incorporated by reference for any purpose.

Claims

1. In a two-part composition for forming an adhesive, A first portion containing an oxirane-containing compound, and The second part contains an acidic phosphorus-based curing agent. A two-part composition comprising, preferably, when the oxirane-containing compound and the acidic phosphorus-based curing agent are mixed at a temperature of about 0°C to 50°C (for example, at room temperature (i.e., about 20°C to 25°C)), gels within about 10 minutes, more preferably within about 5 minutes, and even more preferably within about 1 minute.

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

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.

4. The two-part composition according to claim 1 or claim 2, wherein the aliphatic disubstituted oxirane has more than 2 functionalities.

5. The aliphatic disubstituted oxirane is (i) Unsaturated natural oils, preferably polyunsaturated natural oils, and / or (ii) Elastomer A two-part composition according to claim 1 or claim 2, derived from the peracid epoxidation of the following.

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

7. The two-part composition according to claim 5, wherein the elastomer comprises polybutadiene and / or natural rubber.

8. The two-part composition according to claim 1 or claim 2, wherein the acidic phosphorus-based curing agent comprises an inorganic acid, an organophosphorus compound, or a blend of both.

9. The two-part composition according to claim 8, wherein the inorganic acid comprises phosphoric acid, polyphosphoric acid, subphosphoric acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof.

10. The two-part composition according to claim 8, wherein the organophosphorus compound comprises an alcohol-derived phosphate ester, an aliphatic epoxy-derived phosphate ester, an aromatic epoxy-derived phosphate ester, or any combination thereof.

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 monofunctional or polyfunctional, preferably polyfunctional.

12. The two-part composition according to claim 1 or claim 2, wherein both the aliphatic disubstituted oxirane and the acidic phosphorus-based curing agent are polyfunctional.

13. The two-part composition according to claim 10, wherein the alcohol-derived phosphate ester is formed by the reaction of n-butanol with polyphosphate, the aliphatic epoxy-derived phosphate ester is formed by the reaction of 2-ethylhexylglycidyl ether with phosphoric acid, and the aromatic epoxy-derived phosphate ester is formed by the reaction of phenylglycidyl ether with phosphoric acid.

14. The two-part composition according to claim 1 or claim 2, wherein the aliphatic disubstituted oxirane and the acidic phosphorus-based curing agent are mixed in a stoichiometric ratio of about 1.5:1 to 1:1.5, more preferably about 1:

1.

15. A two-part composition according to claim 1 or claim 2, which is thermosetting.

16. A two-part composition according to claim 1 or claim 2, further comprising a foaming agent.

17. A first portion comprising an aliphatic disubstituted oxirane, and The second part contains an acidic phosphorus-based curing agent. Includes, Preferably, the mixture of the first and second portions is cured within about 10 minutes, more preferably within about 5 minutes, and even more preferably within about 1 minute, at a temperature of about 0°C to 50°C (for example, at room temperature (i.e., about 20°C to 25°C)). Two-part composition.

18. The two-part composition according to claim 17, which is the two-part composition according to claim 1 or claim 2.

19. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a difunctional aromatic glycidyl ether, a polyfunctional aromatic glycidyl ether, a difunctional aliphatic glycidyl ether, a difunctional aliphatic glycidyl ester, a polyfunctional aromatic glycidylamine, a polyfunctional aliphatic glycidyl ether, a polyfunctional peracid epoxy, or any combination thereof.

20. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a bifunctional aromatic glycidyl ether, and the bifunctional aromatic glycidyl ether is preferably a bisphenol F epoxy resin and / or a bisphenol A epoxy resin.

21. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a polyfunctional aromatic glycidyl ether, and the polyfunctional aromatic glycidyl ether is an epoxyphenol novolac resin.

22. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a difunctional aliphatic glycidyl ether, and the difunctional aliphatic glycidyl ether is preferably a glycidyl ether of butanediol.

23. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a bifunctional aliphatic glycidyl ester, and the bifunctional aliphatic glycidyl ester is preferably a glycidyl ester of a dimerized fatty acid.

24. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a polyfunctional aromatic glycidylamine, and the polyfunctional aromatic glycidylamine is preferably a glycidylamine of methylenedianiline.

25. The two-part composition according to claim 17, wherein the oxirane-containing compound comprises a polyfunctional aliphatic glycidyl ether, and the polyfunctional aliphatic glycidyl ether is preferably a castor oil glycidyl ether.

26. The oxirane-containing compound comprises a polyfunctional peracid epoxy, and this polyfunctional peracid epoxy is preferably, (i) Unsaturated natural oils, preferably polyunsaturated natural oils, and / or (ii) Elastomer A two-part composition according to claim 17, derived from the peracid epoxidation of the following.

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

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

29. The two-part composition according to claim 19 or claim 20, wherein the polyfunctional peracid epoxy has more than two functionalities.

30. The two-part composition according to claim 17, wherein the acidic phosphorus-based curing agent comprises an inorganic acid, an organophosphorus compound, or a blend of both.

31. The two-part composition according to claim 30, wherein the inorganic acid comprises phosphoric acid, polyphosphoric acid, subphosphoric acid, pyrophosphoric acid, phosphonic acid, phosphinic acid, or any combination thereof, and the organophosphorus compound comprises an alcohol-derived phosphate ester, an aliphatic epoxy-derived phosphate ester, an aromatic epoxy-derived phosphate ester, or any combination thereof.

32. The two-part composition according to claim 30 or claim 31, wherein the organophosphorus compound is monofunctional or polyfunctional, preferably polyfunctional.

33. The two-part composition according to claim 30 or claim 31, wherein both the oxirane-containing compound and the acidic phosphorus-based curing agent are polyfunctional.

34. The two-part composition according to claim 31, wherein the alcohol-derived phosphate ester is formed by the reaction of n-butanol with polyphosphate.

35. The two-part composition according to claim 31, wherein the aliphatic epoxy-derived phosphate ester is formed by the reaction of 2-ethylhexylglycidyl ether with phosphoric acid, and the aromatic epoxy-derived phosphate ester is formed by the reaction of phenylglycidyl ether with phosphoric acid.

36. The two-part composition according to claim 17, wherein the oxirane-containing compound and the acidic phosphorus-based curing agent are mixed in a stoichiometric ratio of about 1.5:1 to 1:1.5, more preferably about 1:

1.

37. The two-part composition according to claim 17, which is thermosetting.

38. The two-part composition according to claim 17, further comprising a foaming agent.

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