Underwater adhesive method

Abstract

A method of bonding underwater substrates comprising applying a cyanoacrylate composition to at least one substrate underwater and then allowing the composition to cure underwater.

Description

Technical Field

[0001] This invention provides a method for underwater bonding using a curable cyanoacrylate composition. Background Technology

[0002] Curable compositions such as cyanoacrylate adhesives are widely recognized for their excellent ability to quickly bond a variety of substrates, typically in just a few minutes, and sometimes in just a few seconds, depending on the specific substrate.

[0003] Cyanoacrylate adhesive compositions are well-known and widely used as fast-curing, instant adhesives with a wide range of applications. See HV Coover, DW Dreifus, and JT O'Connor, "Cyanoacrylate Adhesives," Handbook of Adhesives, Vol. 27, pp. 463-477, ed. I. Skeist, Van Nostrand Reinhold, New York, 3rd ed. (1990). See also GH Millet, "Cyanoacrylate Adhesives" in Structural Adhesives: Chemistry and Technology, ed. SR Hartshorn, Plenum Press, New York, pp. 249-307 (1986).

[0004] Cyanoacrylate adhesive compositions are well-suited for air curing. Advantageously, these compositions reach operational strength within seconds after air curing and greater than 60% of their original strength within 1 minute after air curing.

[0005] The polymerization of cyanoacrylates is initiated by nucleophiles present on most surfaces under normal atmospheric conditions. Surface chemical initiation refers to the presence of sufficient initiator when two surfaces are in close contact with a thin layer of cyanoacrylate between them. Under these conditions, a strong bond can form in a short time. Therefore, cyanoacrylates essentially act as quick-drying adhesives.

[0006] Cyanoacrylate adhesive compositions are traditionally not used for underwater applications because they are difficult to dispense underwater. It should be understood that underwater means the substrate to be bonded is completely submerged in water. Water is in contact with the substrate. As used herein, "underwater" does not refer to a situation where the substrate is underwater but not in contact with water; for example, underwater does not mean placing the substrate in a waterproof container that is in contact with water while the substrate is not in contact with water because the waterproof container keeps it dry. Specifically, the present invention relates to a method of using a cyanoacrylate adhesive dispensed underwater from a container. In this case, the cyanoacrylate adhesive is dispensed onto the substrate surface via water, and the substrate surface is also in contact with water.

[0007] Dispensing cyanoacrylate adhesive compositions underwater can cause the composition to react with water and cure prematurely before being applied to the substrate to be bonded. In fact, cyanoacrylate compositions are very sensitive to water, and in some cases, even trace amounts of water can cause them to cure prematurely, such as when stored for later use.

[0008] The performance, especially the durability, of cyanoacrylate adhesives is often questioned when exposed to water. Adhesions formed using cured cyanoacrylate compositions may be susceptible to the effects of water. For example, the adhesive may eventually fail due to the degradation of the cured cyanoacrylate composition over time when exposed to water. Generally, exposure to water leads to a loss of adhesive strength over time.

[0009] When cyanoacrylate adhesive compositions are dispensed underwater, they may partially cure before being applied to a first substrate but before being bonded to a second substrate. While adhesion may form between the substrates in this case, the adhesive strength is weak because the composition has already partially cured before bonding.

[0010] To overcome these problems, a cyanoacrylate adhesive composition can typically be applied to a substrate in the air, and then the bonded substrate can be placed underwater.

[0011] For applications where cyanoacrylate adhesive compositions offer superior performance, underwater bonding is highly advantageous. Underwater application and curing of cyanoacrylate adhesive compositions is particularly beneficial in situations where it is difficult to remove the substrate from the water. For example, using cyanoacrylate adhesive compositions to bond underwater ship components during ship repairs would be highly beneficial.

[0012] It would be beneficial to provide alternative adhesives that can: (1) be dispensed in an immersion state; (2) remain uncured for a sufficient time to be applied to the substrate to be bonded; (3) subsequently cure, preferably with a short open time; (4) form a high-strength bond; and (5) maintain bond strength. All of the above requirements must be met underwater. Summary of the Invention

[0013] On one hand, the present invention provides a method for bonding an underwater substrate, comprising: (a) Applying a cyanoacrylate composition to at least one substrate underwater, wherein the cyanoacrylate composition comprises: i. A first portion, the first portion comprising a cyanoacrylate component and a peroxide catalyst; and ii. Part Two, which comprises a free radical curable component and a transition metal, When mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component. (b) Curing the composition underwater.

[0014] Underwater bonding refers to immersing the substrate in water, allowing water to come into contact with the substrate while the composition is being applied. The substrate is not, for example, placed in a waterproof container and therefore not directly exposed to water. Advantageously, this method enables underwater bonding, an operation that is impossible in conventional applications because components cannot be disassembled and dried before bonding.

[0015] Advantageously, the composition applied in this method can be dispensed while submerged and left uncured for a sufficiently long time to be applied to the substrate to be bonded; subsequently, it cures within a short curing time. Advantageously, the cured composition cured underwater forms a high-strength bond and maintains this bond strength over time. Ideally, the composition has a sufficiently long open time to be dispensed, applied, and bonded to the substrate before curing, but the curing time is faster than compositions used in previous methods to minimize the time the user spends underwater.

[0016] The cyanoacrylate blends disclosed herein overcome the drawbacks of using cyanoacrylate compositions for bonding underwater substrates. The cyanoacrylate compositions used in the methods of this invention are curable. All desirable properties of this invention refer to the performance of the composition in an underwater environment. The compositions of this invention remain in situ upon dispensing. The compositions of this method can be dispensed underwater, for example, without premature curing upon initial contact with water, thus preventing the dispensing of the composition onto the substrate. In cases of initial contact with water but without curing throughout the volume of the composition, a skin may form, thus preventing dispensing. The compositions of this method can have a suitable viscosity to allow for dispensing. The compositions can have suitable buoyancy. For example, it is appropriate that the components of this method do not shift due to forces caused by normal water flow.

[0017] This composition can be dispensed underwater and used in methods of bonding underwater substrates. While not bound by theory, it is believed that unexpected open times may occur in aqueous environments due to the moderating effect of the acrylate portion of the mixture on the curing rate, coupled with the inherently high viscosity of the material. The cone-plate viscosity of the first portion of the composition can be 4000 to 11000 mPa·s. The cone-plate viscosity of the second portion can be 45000 to 75000 mPa·s.

[0018] The cyanoacrylate composition can be applied at a volume ratio of approximately 1:1 between the first part and the second part.

[0019] A method for bonding underwater substrates may include exposing the composition to water for up to 45 seconds before bonding the surface of the second substrate to the coated surface of the first substrate. This may be referred to as the open time of the composition. The composition may have a good open time of up to 90 seconds, for example up to 60 seconds, or for example up to 45 seconds. Advantageously, a good open time allows the substrates time to properly assemble before the composition cures. Because a good open time provides assembly time, the substrates can be assembled into components in the correct configuration. The composition has a good open time and allows for underwater nozzle replacement (through which the composition is dispensed) without composition curing. The composition can form a film on the top layer of a membrane but does not cure in the bulk and has a good open time.

[0020] In underwater substrate bonding methods, the composition does not mix with water (e.g., in a water column) nor is it otherwise dispersed in water. The physical properties of the composition (e.g., its viscosity) prevent it from mixing with water and allow it to remain at the point of application. The outermost layer of the composition can cure to form a thin film, thereby preventing the bulk of the composition from contacting water. Therefore, full-volume curing of the composition can occur after the two substrates are bonded together.

[0021] In the method of bonding underwater substrates, one or both substrates can be metal, for example, one or both substrates can be steel.

[0022] In the method of bonding an underwater substrate, at least one substrate may include a material selected from the following: steel, aluminum, wood, plastic, glass fiber, building materials (including aggregates), sand, concrete / cement materials (including wire mesh cement), and fiber-reinforced plastics.

[0023] Appropriately, the two substrates may independently comprise materials selected from: steel, aluminum, wood, plastic, fiberglass, building materials (including aggregates), sand, concrete / cement materials (including wire mesh cement), and fiber-reinforced plastics.

[0024] In methods of bonding underwater substrates, at least one substrate can be a vessel, such as a small boat or ship, or a portion thereof. This method can be used to secure items to a small boat or ship, for example, to install sensors or connect replacement parts, or for servicing the small boat or ship. Using the method of this invention, this operation can be accomplished without returning to land to remove the small boat or ship from the water.

[0025] In methods of bonding underwater substrates, at least one substrate can be a structure located underwater or part of a structure extending underwater, such as bridges, oil or gas drilling equipment, pipelines, dams, wind turbines, etc. These structures cannot be removed from the water, making it highly advantageous to be able to secure items (e.g., fittings, sensors, or replacement parts) or perform repairs underwater.

[0026] In the method of bonding underwater substrates, one or both substrates may be metal. In the method of bonding underwater substrates, one or both substrates may be plastic materials.

[0027] In methods for bonding underwater substrates, the nozzle life can be at least 4 minutes, for example, at least 5 minutes. The dispensing nozzle exhibits good nozzle life because the composition does not cure prematurely and clog the nozzle. This is surprising, as compositions containing cyanoacrylates typically cure rapidly when exposed to moisture (e.g., when underwater). Advantageously, the extended nozzle life allows for the application of more composition before nozzle replacement.

[0028] The method for bonding underwater substrates can be carried out in water containing varying amounts of salt and / or minerals. For example, the method can be carried out in distilled water or treated water (e.g., public / tap water). The method can also be carried out in fresh water, such as well water, rivers, or lakes. The method can also be carried out in saline water, such as seawater, for example in water with a salinity of about 30 g / L to about 50 g / L.

[0029] The method of bonding underwater substrates can be carried out in water with a pH range of about 6 to about 9 (e.g., about 6.5 to about 8 or about 7.5 to about 8.5).

[0030] In methods for bonding underwater substrates, peroxide catalysts may include perbenzoate esters.

[0031] The present invention further provides the use of cyanoacrylate compositions for underwater adhesive substrates, wherein the composition comprises: The first part comprises a cyanoacrylate component and tert-butyl perbenzoate as a peroxide catalyst, wherein the content of tert-butyl perbenzoate is from about 0.01% to about 10% by weight of the cyanoacrylate component; and The second part contains a free radical curable component and a transition metal. The cyanoacrylate component comprises H2C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl, and wherein when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component.

[0032] The present invention also provides a component comprising two underwater substrates bonded together by a cyanoacrylate composition comprising: The first part comprises a cyanoacrylate component and tert-butyl perbenzoate as a peroxide catalyst, wherein the content of tert-butyl perbenzoate is from about 0.01% to about 10% by weight of the cyanoacrylate component; and The second part contains a free radical curable component and a transition metal. The cyanoacrylate component comprises H₂C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl, and wherein, when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component. It should be understood that the assembly comprises two substrates bonded together by curing the cyanoacrylate composition.

[0033] In the components of this invention, one or both substrates may be metal. One or both substrates may be steel.

[0034] In the components of this invention, one or both substrates may be plastic materials. Detailed Implementation

[0035] A method for bonding an underwater substrate includes applying the composition disclosed herein to at least one substrate underwater and then allowing the composition to cure.

[0036] The nozzle life can be at least 4 minutes, for example, at least 5 minutes. This means that during the application of the composition, the composition will not cure within the nozzle used to dispense the composition during this time. A thin layer of composition may cure at the nozzle tip where the composition is in contact with water. The body of the composition in the nozzle that is not in contact with water will remain uncured. Because the composition has a good nozzle life underwater, it can still be dispensed from the nozzle.

[0037] Advantageously, the composition can be exposed to water (e.g., immersed in water) for up to 45 seconds before the surface of the second substrate is bonded to the coated surface of the first substrate, and the composition will remain uncured, thereby forming an adhesive between the substrates.

[0038] This method involves curing the composition underwater. There is no need to remove the composition from the water for curing. The cured adhesive strength is high. This cured adhesive strength can be maintained over time, making the method of this invention suitable for long-term bonding of substrates. Part A of the composition

[0039] The cyanoacrylate component comprises a cyanoacrylate monomer. The cyanoacrylate component may contain H₂C=C(CN)-COOR, where R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl groups, for example, where R is selected from C₂C₃C₄ ...�C₃C₄C₄C₄C₄C₄C₄C₄C₄C₄C₄ 1-15 Alkyl, C 2-15 Alkoxyalkyl, C 3-15 cycloalkyl, C 2-15 alkenyl, C 7-15 Aryl alkyl, C 6-15 Aryl, C 3-15 Allyl and C 1-15 Halogenated alkyl group. Preferably, the cyanoacrylate monomer is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate (“EGA”), propyl cyanoacrylate, butyl cyanoacrylate (e.g., n-butyl-2-cyanoacrylate), octyl cyanoacrylate, allyl cyanoacrylate, β-methoxyethyl cyanoacrylate, and combinations thereof. Ethyl-2-cyanoacrylate is particularly preferred.

[0040] The cyanoacrylate component may be present in the composition of part A from about 50% to about 99.98% by weight, for example, preferably from about 90% to about 99% by weight, and particularly preferably from about 92% to about 97% by weight of the composition of part A.

[0041] The peroxide catalyst included in the composition of part A of the two-part binder system can be tert-butyl perbenzoate.

[0042] Typically, the amount of peroxide catalyst should be from about 0.001% to about 10.00% by weight of the composition, ideally from about 0.01% to about 5.00% by weight of the composition, for example, from about 0.50 to 2.50% by weight of the composition.

[0043] Additives can be added to the A-component composition of the adhesive system to improve physical properties, such as increasing setting speed, improving shelf-life stability, flexibility, thixotropy, increasing viscosity, improving color, and improving toughness. Therefore, such additives can be selected from accelerators, free radical stabilizers, anionic stabilizers, gelling agents, thickeners [such as PMMAs], thixotropic agents (such as fumed silica), dyes, toughening agents, plasticizers, and combinations thereof.

[0044] One or more accelerators may also be used in the adhesive system (especially in the composition of part A) to accelerate the curing of the cyanoacrylate component. Such accelerators may be selected from calixarenes, oxacalixarenes, silanol crown ethers, crown ethers, cyclodextrins, polyethylene glycol di(meth)acrylates, ethoxylated hydroxy compounds, and combinations thereof.

[0045] Many calixarenes and oxacalixarenes are known and have been reported in patent literature. For example, see U.S. Patent Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966 and 4,855,461, the disclosures of which are hereby incorporated herein by reference.

[0046] For example, regarding calixarenes, compounds having the following structures are applicable in this paper: Where R 1 It is an alkyl, alkoxy, substituted alkyl, or substituted alkoxy group; R 2 It is H or alkyl; n is 4, 6 or 8.

[0047] A particularly desirable calixarene is tetrabutyltetra[2-ethoxy-2-oxoethoxy]calix-4-aromatic.

[0048] Many crown ethers are known. Examples, which can be used alone or in combination, include 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asymmetric dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decyl-15-crown-5, and 1,2-naphtho- -15-crown-5, 3,4,5-naphthyl-16-crown-5, 1,2-methylbenzo-18-crown-6, 1,2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1,2-tert-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-tert-butylcyclohexyl-18-crown-6, asymmetric dibenzo-22-crown-6, and 1,2-benzo-1,4-benzo-5-oxo-20-crown-7. See U.S. Patent No. 4,837,260 (Sato), the disclosure of which is expressly incorporated herein by reference.

[0049] Many silicone crown ether compounds are known and have been reported in the literature. For example, a typical silicone crown ether compound can be represented by the following structure: Where R 3 and R 4 It is an organic group that does not itself cause the polymerization of cyanoacrylate monomers, R 5 It is H or CH3, and n is an integer between 1 and 4. A suitable R... 3 and R 4 Examples of groups include the R group, alkoxy groups (e.g., methoxy groups), and aryloxy groups (e.g., phenoxy groups). 3 and R 4 The group can contain halogens or other substituents, such as trifluoropropyl. However, it is not suitable as an R 4 and R 5 The group is a basic group, such as amino, substituted amino, and alkylamino.

[0050] Specific examples of silicone crown ether compounds that can be used in the compositions of the present invention include: See, for example, U.S. Patent No. 4,906,317 (Liu), the disclosure of which is hereby expressly incorporated herein by reference.

[0051] Various cyclodextrins can be used in this invention. For example, the cyclodextrin described and claimed in U.S. Patent No. 5,312,864 (Wenz), the disclosure of which is hereby incorporated by reference. Hydroxyl derivatives of α, β, or γ-cyclodextrins (α, β, or γ-cyclodextrins) that are at least partially soluble in cyanoacrylates are suitable choices for use as promoter components herein.

[0052] Furthermore, the poly(ethylene glycol) di(meth)acrylates applicable to this document include those within the following structures: Where n is greater than 3, for example, in the range of 3 to 12, n of 9 is particularly desirable. More specific examples include PEG 200 DMA (where n is approximately 4), PEG 400 DMA (where n is approximately 9), PEG 600 DMA (where n is approximately 14), and PEG 800 DMA (where n is approximately 19), where the number (e.g., 400) represents the average molecular weight of the diol moiety (excluding the two methacrylate groups) in the molecule, expressed in grams per mole (i.e., 400 g / mol). A particularly desirable PEG DMA is PEG cC400 DMA.

[0053] And ethoxylated hydroxyl compounds (or usable ethoxylated fatty alcohols), which can be selected from the following structures: Where C m It can be a straight-chain or branched alkyl or alkenyl chain, m is an integer between 1 and 30, for example 5 to 20, n is an integer between 2 and 30, for example 5 to 15, and R can be H or alkyl, for example C 1-6 alkyl.

[0054] In addition, the accelerator contains the following structure: Where R represents hydrogen and C 1-6 Alkyl, C 1-6 Alkoxy, alkyl sulfides, haloalkyl, carboxylic acids and their esters, sulfinic acids, sulfonic acids and sulfurous acids and their esters, hypophosphonic acids, phosphonic acids and phosphorous acids and their esters, Z is a polyether bond, n is 1-12 and p is 1-3, as defined above, and R' is the same as R, g is the same as n.

[0055] A particularly ideal accelerator component in this category is Where the sum of n and m is greater than or equal to 12.

[0056] The accelerator may be present in the composition in the range of about 0.01% by weight to about 10% by weight, preferably in the range of about 0.1% to about 0.5% by weight, and particularly preferably about 0.4% by weight of the total composition.

[0057] The stabilizers used in the A-part composition of the adhesive system include free radical stabilizers, anionic stabilizers, and stabilizer packages comprising combinations thereof. The types and amounts of such stabilizers are well known to those skilled in the art. See, for example, U.S. Patent Nos. 5,530,037 and 6,607,632, the disclosures of which are incorporated herein by reference. Commonly used free radical stabilizers include hydroquinone, while commonly used anionic stabilizers include boron trifluoride, boron trifluoride diethyl ether compounds, sulfur trioxide (and its hydrolysis products), and methanesulfonic acid. Part B of the composition

[0058] Free radical curable monomers used in Part B compositions of adhesive systems include (meth)acrylate monomers, compounds containing maleimide, itacamide, or nadiimide, and combinations thereof.

[0059] The (meth)acrylate monomers used in part B of the adhesive system comprise a variety of (meth)acrylate monomers, some of which are aromatic, others aliphatic, and still others alicyclic. Examples of such (meth)acrylate monomers include difunctional or trifunctional (meth)acrylates, such as polyethylene glycol dimethacrylate, tetrahydrofuran (meth)acrylate and dimethacrylate, hydroxypropyl methacrylate (“HPMA”), hexanediol dimethacrylate, trimethylolpropane trimethacrylate (“TMPTMA”), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (“TRIEGMA”), benzyl methacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, etc. Dimethacrylates, di(pentanediol)dimethacrylates, tetraethylene glycol diacrylates, diglycerol tetramethacrylates, tetramethylene dimethacrylates, ethylene dimethacrylates, neopentane glycol diacrylates, trimethylolpropane triacrylates, and bisphenol-A mono- and bis(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate (“EBIPMA”), bisphenol-F mono- and bis(meth)acrylates, such as ethoxylated bisphenol-F (meth)acrylate, and methacrylate-functionalized polyurethanes.

[0060] Maleimide, nadiimide, and itaconiimide include compounds having structures I, II, and III, respectively. Where: m = 1-15, p = 0-15, each R 2 Independently selected from hydrogen or lower alkyl groups, and J is a monovalent or polyvalent portion containing an organic group or an organosiloxane group and combinations of two or more of them.

[0061] More specific representatives of maleimides, itaconimides, and nadiimides include those corresponding to structures I, II, or III, where m = 1–6, p = 0, R 2Independently selected from hydrogen or lower alkyl groups, and J is a monovalent or polyvalent group selected from: hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group, alkylene group, substituted alkylene group, heteroatom-containing alkylene group, substituted heteroatom-containing alkylene group, polysiloxane, polysiloxane polyurethane block copolymer, and combinations of two or more thereof, optionally containing a linker selected from: covalent bond, -O-, -S-, -NR-, -OC(O)-, -OC(O)-O-, -OC(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -SC(O)-, -SC(O)-O-, -SC(O)-NR-, -S(O)-, -S(O)2-, -OS(O)2-, -OS(O)2-O-, -OS(O)2-NR-, -OS(O)-, -OS(O)-O-, -OS(O)-NR-, -O-NR-C(O)-, -O-NR-C(O)-O-, -O-NR-C(O)-NR-, -NR-OC(O)-, -NR-OC(O)-O-, -NR-OC(O)-NR-, -O-NR-C(S)-, -O-NR-C(S)-O-, -O-NR-C(S)-NR-, -NR-OC(S)-, -NR-OC(S)-O-, -NR-OC(S)-NR-, -OC(S)-, -OC(S)-O-, -OC(S)-NR-, -NR-C(S)-, -NR-C(S)-O-, -NR-C(S)-NR-, -SS(O)2-, -SS(O)2-O-, -SS(O)2-NR-, -NR-OS(O)-, -NR-OS(O)-O-, -NR-OS(O)-NR-, -NR-OS(O)2-, -NR-OS(O)2-O-, -NR-OS(O)2-NR-, -O-NR-S(O)-, -O-NR-S(O)-O-, -O-NR-S(O)-NR-, -O-NR-S(O)2-O-, -O-NR-S(O)2-NR-, -O-NR-S(O)2-, -OP(O)R2-, -SP(O)R2-, -NR-P(O)R2-, wherein each R is independently hydrogen, alkyl or substituted alkyl, and any combination of two or more thereof.

[0062] When one or more of the aforementioned monovalent or polyvalent groups include one or more of the aforementioned linking groups to form a "J"-shaped appendage of a maleimide, nadiimide, or itaconiimide group, as readily recognized by those skilled in the art, a variety of linking groups can be generated, such as oxoalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxenyl, thioenyl, aminoenyl, carboxylenyl, oxynyl, thioynyl, aminoynyl, carboxylynyl, oxocycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxylcycloalkyl, oxocycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxylcycloalkyl, oxocycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxylcycloalkyl, heterocycle, oxoheterocycle, thioheterocycle, aminoheterocycle, carboxylheterocycle, oxaryl, thioaryl, aminoaryl. Carboxyaryl, heteroaryl, oxaaryl, thioaaryl, aminoheteroaryl, carboxyheteroaryl, oxoalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxoarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxoarylenyl, thioarylenyl, aminoarylenyl, carboxyarylenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl, carboxyalkenylaryl, oxyalkenylynyl, thioarylynyl, aminoarylynyl, carboxyarylynyl, oxyalkenylynyl, thioylynyl, aminoylynyl or carboxyylynyl, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenyl, thioalkylene Alkenyl, amino-imenyl, carboxy-imenyl, oxy-imyneyl, thio-imyneyl, amino-imyneyl, carboxy-imyneyl, oxy-cycloalkyl, thio-cycloalkyl, amino-cycloalkyl, carboxy-cycloalkyl, oxy-cycloalkyl, thio-cycloalkyl, amino-cycloalkyl, carboxy-cycloalkyl, oxy-aryl, thio-aryl, amino-aryl, carboxy-aryl, oxyalkyl, oxoalkylaryl, thio-arylalkyl, thioalkylaryl, amino-alkylaryl, carboxy-alkylaryl, oxo-arylalkyl, thio-arylalkyl, amino-arylalkyl, carboxy-arylalkyl, oxo-arylalkyl, thio-arylalkyl, amino-arylalkyl, carboxy-arylalkyl, oxo-arylalkyl, thio-arylalkyl, amino-arylalkyl, carboxy-arylalkyl Oxylenyl arylene, thiolenyl arylene, aminolenyl arylene, carboxyllenyl arylene, oxylenyl arylene, thiolenyl arylene, aminolenyl arylene, carboxyl arylene, oxylenyl arylene, thiolenyl arylene, aminolenyl arylene, carboxyl arylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene, carboxylheteroarylene, divalent or polyvalent cyclic moieties containing heteroatoms, divalent or polyvalent cyclic moieties containing oxy heteroatoms, divalent or polyvalent cyclic moieties containing sulfur heteroatoms, divalent or polyvalent cyclic moieties containing amino heteroatoms, divalent or polyvalent cyclic moieties containing carboxyl heteroatoms, disulfides, sulfonamides, etc.

[0063] In another embodiment, maleimide, nadiimide and itaconiimide intended for use in the practice of the present invention are intended to have structures I, II and III, wherein m = 1-6, p = 0-6, and J is selected from saturated straight-chain alkyl or branched alkyl, optionally containing an optionally substituted aryl moiety as a substituent on the alkyl chain or as part of the alkyl chain backbone, and wherein the alkyl chain has a maximum of about 20 carbon atoms. Siloxanes having the following structures: -(C(R) 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -, -(C(R 3 )2) d -C(R 3 )-C(O)O-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -O(O)C-(C(R 3 )2) e -, or -(C(R 3 )2) d -C(R 3 )-O(O)C-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -C(O)O-(C(R 3 )2) e -, where: each R 3 Independently hydrogen, alkyl, or substituted alkyl; each R 4 Independently hydrogen, lower alkyl or aryl; d = 1-10; e = 1-10; and f = 1-50; Polyepoxides having the following structure: [(CR2)] r -O-] f -(CR2) s - where: each R is independently hydrogen, alkyl, or substituted alkyl; r = 1-10; s = 1-10; and f is as defined above; Aromatic groups with the following structures: Wherein: each Ar is a monosubstituted, disubstituted, or trisubstituted aromatic or heteroaromatic ring having 3 to 10 carbon atoms; and Z is: a saturated straight-chain alkylene or branched alkylene, optionally containing a saturated cyclic moiety as a substituent on the alkylene chain or as part of the alkylene chain backbone, or Polyepoxides having the following structure: -[(CR2)] r -O-] q -(CR2) s - where: each R is independently hydrogen, alkyl, or substituted alkyl; r and s are each defined as above; and q is in the range of 1 to 50; Di- or tri-substituted aromatic moieties having the following structures: Wherein: each R is independently hydrogen, alkyl, or substituted alkyl; t is in the range of 2 to 10; u is in the range of 2 to 10; and Ar is defined as above; Aromatic groups having the following structures: Wherein: each R is independently hydrogen, alkyl, or substituted alkyl; t=2-10, k = 1, 2, or 3 g = 1 to approximately 50, Each Ar is as defined above. E is either -O- or -NR 5 -, where R 5 It is hydrogen or a lower alkyl group; and W is a straight-chain or branched alkyl, alkylene, oxoalkylene, alkenyl, alkenyl, oxoalkene, ester, or polyester, and is a siloxane with the following structure: -(C(R) 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -, -(C(R 3 )2) d -C(R 3 )-C(O)O-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e-O(O)C-(C(R 3 )2) e -, or -(C(R) 3 )2) d -C(R 3 )-O(O)C-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -C(O)O-(C(R 3 )2) e - where: each R 3 Independently hydrogen, alkyl, or substituted alkyl, each R 4 It is independently hydrogen, a lower alkyl or aryl, d=1-10, e=1-10, and f=1-50; Polyepoxides having the following structure: -[(CR2)] r -O-] f -(CR2) s - where: each R is independently hydrogen, alkyl or substituted alkyl; r = 1-10; s = 1-10; and f is defined as above; optionally containing a substituent selected from hydroxyl, alkoxy, carboxyl, nitrile, cycloalkyl or cycloalkenyl; Carbamate groups with the following structures: R 7 -UC(O)-NR 6 -R 8 -NR 6 -C(O)-(OR 8 -OC(O)-NR 6 -R 8 -NR 6 -C(O)) v -UR 8 - Where: each R 6 Independently hydrogen or lower alkyl; each R 7 Independently, it is an alkyl, aryl, or aralkyl group having 1 to 18 carbon atoms; each R 8 It is an alkyl or alkoxy chain having a maximum of about 100 atoms, optionally substituted with Ar; U is -O-, -S-, -N(R)-, or -P(L). lf2 - where R is as defined above, and each L is independently =O, =S, -OR, or -R; and v = 0-50; Polycyclic alkenyl groups; or mixtures of any two or more thereof.

[0064] In a more specific description of compounds containing maleimide, nadiimide, and itaconitumide of structural formulas I, II, and III, each R is independently hydrogen or a lower alkyl group (e.g., C10). 1-4 ), -J- includes branched alkyl, alkylene, epoxide, alkylene carboxyl or alkylene amide groups, having sufficient length and branching to make maleimide, nadiimide and / or itaconiimide compounds liquid, and m is 1, 2 or 3.

[0065] Particularly desirable maleimide-containing compounds include those having two maleimide groups and an aromatic group (e.g., phenyl, biphenyl, diphenyl, or naphthyl bond) between them.

[0066] In addition to the radical-curable component, part B also contains transition metal compounds. Non-exhaustive examples of transition metal compounds include copper, vanadium, cobalt, and iron compounds. For example, for copper compounds, copper compounds in the 1+ or 2+ valence state are preferred. Non-exhaustive examples of such copper (I) and (II) compounds include copper(II) hydrate of 3,5-diisopropylsalicylate, bis(2,2,6,6-tetramethyl-3,5-heptadecyl)copper, basic copper phosphate (II), copper chloride (II), copper acetate monohydrate (II), copper tetra(acetonitrile)hexafluorophosphate (I), copper formate (II) hydrate, copper tetraacetonitrile trifluoromethanesulfonate (I), copper tetrafluoroborate (II), copper perchlorate (II), copper tetra(acetonitrile)tetrafluoroborate (I), copper hydroxide (II), copper hexafluoroacetylacetonate (II) hydrate, and copper carbonate (II). The amount of these copper (I) and (II) compounds used is such that when dissolved or suspended in a carrier (e.g., (meth)acrylate), the concentration in the solution or suspension is from about 100 ppm to about 5,000 ppm, for example from about 500 ppm to about 2,500 ppm, for example from about 1,000 ppm.

[0067] As for vanadium compounds, vanadium compounds having vanadium in 2+ and 3+ valence states are preferred. Examples of such vanadium(III) compounds include vanadium naphthenate and vanadium acetylacetonate. The amount of these vanadium(III) compounds can be from 50 ppm to about 5,000 ppm, for example from about 500 ppm to about 2,500 ppm, for example from about 1,000 ppm.

[0068] As for cobalt compounds, compounds in which cobalt is in the 2+ valence state are preferred. Examples of such cobalt(II) compounds include cobalt cobalt naphthenate, cobalt tetrafluoroborate, and cobalt acetylacetonate. The amount of these cobalt(II) compounds can range from about 100 ppm to about 1000 ppm.

[0069] As for iron compounds, compounds in which iron is in the 3+ valence state are preferred. Examples of such iron(III) compounds include ferric acetate, ferric acetylacetone, ferric tetrafluoroborate, ferric perchlorate, and ferric chloride. The amount of these iron compounds used is approximately 100 ppm to 1000 ppm.

[0070] As mentioned above, either or both of the A or B components may contain additives to influence various performance characteristics.

[0071] The fillers intended to be used include, for example, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesium oxide, silica (e.g., fumed silica or fused silica), alumina, perfluorocarbon polymers (e.g., TEFLON®), thermoplastic polymers, thermoplastic elastomers, mica, glass powder, etc. The particle size of these fillers is preferably about 20 micrometers or smaller.

[0072] For silica, silica can have an average particle size of nanoparticle size; that is, approximately 10. -9 The average particle size is in meters. Silica nanoparticles can be pre-dispersed in epoxy resins and are available from Nanoresins GmbH, Germany, under the trade name NANOCRYL. NANOCRYL is the trade name for a series of silica nanoparticle-reinforced (meth)acrylate products. The silica phase consists of surface-modified synthetic SiO2 nanospheres with a diameter less than 50 nanometers and an extremely narrow particle size distribution. The SiO2 nanospheres are dispersed in a non-agglomerated state within the (meth)acrylate matrix, resulting in a low viscosity of the resin containing up to 50% by weight of silica.

[0073] Based on the total weight of the composition, the amount of silica component may be from about 1 to about 60% by weight, for example from about 3 to about 30% by weight, ideally from about 5 to about 20% by weight.

[0074] Toughening agents particularly intended for use in the Part A compositions include elastic polymers selected from elastic copolymers of low-carbon olefin monomers with (i) acrylates, (ii) methacrylates, or (iii) vinyl acetate, such as acrylic rubbers; polyester polyurethanes; ethylene-vinyl acetate; fluorinated rubbers; isoprene-acrylonitrile polymers; chlorosulfonated polyethylene; and homopolymers of polyvinyl acetate, which have been found particularly useful. [See U.S. Patent No. 4,440,910 (O'Connor), each disclosure of which is incorporated herein by reference]. The '910 patent describes elastic polymers that are either homopolymers of alkyl acrylates; or copolymers of another polymerizable monomer (e.g., a low-carbon olefin) with alkyl acrylates or alkoxy esters; and copolymers of alkyl acrylates or alkoxy esters. Other unsaturated monomers that can be copolymerized with alkyl acrylates and alkoxy esters include dienes, active halogenated unsaturated compounds, and other acrylic monomers such as acrylamides.

[0075] For example, one group of such elastomer polymers is a copolymer of methyl acrylate and ethylene produced by DuPont under the product name VAMAC, such as VAMAC N123 and VAMAC B-124. According to DuPont, VAMAC N123 and VAMAC B-124 are masterbatches for ethylene / acrylate elastomers. DuPont's VAMAC G material is a similar copolymer but does not contain fillers or stabilizers for coloring. VAMAC VCS rubber appears to be a base rubber from which other members of the VAMAC product family are blended. VAMAC VCS (also known as VAMAC MR) is a reaction product of a combination of ethylene, methyl acrylate, and monomers with carboxylic acid curing sites, which, once formed, are substantially free of processing aids (such as release agents octadecylamine, complex organophosphates, and / or stearic acid) and antioxidants (such as substituted diphenylamine).

[0076] DuPont markets rubbers made from ethylene and methyl acrylate under the trade names VAMAC VMX 1012 and VCD 6200. It is believed that the polymer backbone of VAMAC VMX 1012 rubber contains little to no carboxylic acids. Like VAMAC VCS rubber, VAMAC VMX 1012 and VCD 6200 rubbers are essentially free of processing aids such as the mold release agent octadecylamine, complex organophosphates and / or stearic acid, and antioxidants such as substituted diphenylamine, as described above. All of these VAMAC elastomer polymers are suitable for use here.

[0077] In addition, the composition in part A may also contain vinylidene chloride-acrylonitrile copolymer [see U.S. Patent No. 4,102,945 (Gleave)] and vinyl chloride / vinyl acetate copolymer [see U.S. Patent No. 4,444,933 (Columbus)]. The disclosures of these U.S. patents are incorporated herein by reference in their entirety.

[0078] The copolymer of polyethylene and polyvinyl acetate is useful and is commercially available from LANXESS Limited under the trade name LEVAMELT.

[0079] Several LEVAMELT brand copolymers are available, including, for example, LEVAMELT 400, LEVAMELT 600, and LEVAMELT 900. LEVAMELT products vary depending on the vinyl acetate content. For example, LEVAMELT 400 contains an ethylene-vinyl acetate copolymer with a vinyl acetate content of 40% by weight. LEVAMELT products are supplied in granular form. The granules are nearly colorless and dusted with silica and talc. LEVAMELT consists of methylene units forming a saturated backbone with side acetate groups. The presence of a fully saturated backbone indicates that LEVAMELT brand copolymers are particularly stable; they contain no reactive double bonds, whereas conventional rubbers are prone to aging reactions and are susceptible to ozone and UV radiation. The saturated backbone is reported to make the polymer robust and durable.

[0080] Interestingly, depending on the polyethylene / polyvinyl acetate ratio, the solubility of these LEVAMELT elastomers varies in different monomers, and the toughening ability also varies with the solubility.

[0081] LEVAMELT elastomers are in particulate form and are easier to formulate than other known elastomer toughening agents.

[0082] VINNOL surface coating resins, offered by Wacker Chemie AG in Munich, Germany, represent a range of vinyl chloride-derived copolymers and terpolymers suitable for various industrial applications. The main components of these polymers are different combinations of vinyl chloride and vinyl acetate. Terpolymers in the VINNOL product line also contain carboxyl or hydroxyl groups. These vinyl chloride / vinyl acetate copolymers and terpolymers are also available.

[0083] Carboxyl-containing VINNOL surface coating resins are terpolymers of vinyl chloride, vinyl acetate, and dicarboxylic acid, varying in molar composition, degree of polymerization, and polymerization process. These terpolymers have reportedly exhibited excellent adhesion, particularly on metal substrates.

[0084] VINNOL surface coating resins with hydroxyl groups are copolymers and terpolymers of vinyl chloride, hydroxy acrylate and dicarboxylic acid ester, with varying compositions and degrees of polymerization.

[0085] VINNOL surface coating resin without functional groups is a copolymer of vinyl chloride and vinyl acetate with different molar compositions and degrees of polymerization.

[0086] It may also contain rubber particles, especially rubber particles with a relatively small average particle size (e.g., less than about 500 nanometers or less than about 200 nanometers), particularly those included in part B of the composition. The rubber particles may or may not have a shell, as is commonly known in core-shell structures.

[0087] For rubber particles with a core-shell structure, such particles typically have a core made of a polymeric material with elastic or rubbery properties (i.e., a glass transition temperature below about 0°C, for example, below about -30°C), which is surrounded by a shell made of a non-elastic polymeric material (i.e., a glass transition temperature above ambient temperature, for example, above about 50°C). For example, the core may be made of diene homopolymers or copolymers (e.g., homopolymers of butadiene or isoprene, copolymers of butadiene or isoprene with one or more olefinically unsaturated monomers (e.g., vinyl aromatic monomers, (meth)acrylonitrile, (meth)acrylates, etc.), while the shell may be made of a polymer or copolymer of one or more monomers with a higher glass transition temperature, such as (meth)acrylates (e.g., methyl methacrylate), vinyl aromatic monomers (e.g., styrene), vinyl cyanides (e.g., acrylonitrile), unsaturated acids and anhydrides (e.g., acrylic acid), (meth)acrylamide, etc.). Other rubbery polymers are also suitable for the core material, including polybutyl acrylate or polysiloxane elastomers (such as polydimethylsiloxane, especially cross-linked polydimethylsiloxane).

[0088] Typically, the core will contain about 50 to about 95% by weight of rubber particles, while the shell will contain about 5% to about 50% by weight of rubber particles.

[0089] Preferably, the size of the rubber particles is relatively small. For example, the average particle size can be from about 0.03 to about 2 micrometers, or from about 0.05 to about 1 micrometer. The average diameter of the rubber particles can be less than about 500 nanometers, for example, less than about 200 nanometers. For example, the average diameter of core-shell rubber particles can be in the range of about 25 to about 200 nanometers.

[0090] When used, these core-shell rubbers can toughen the composition, and this toughening usually occurs in a predictable manner (with regard to the temperature neutrality of curing) due to their essentially uniform dispersion, which is typically observed in commercially available core-shell rubbers.

[0091] For rubber particles that do not have this shell, the rubber particles may be based on a core with this structure.

[0092] The rubber particles are expected to be relatively small in size. For example, the average particle size can be from about 0.03 to about 2 μm, or from about 0.05 to about 1 μm. In some embodiments of the invention, the average diameter of the rubber particles is less than about 500 nm. In other embodiments, the average particle size is less than about 200 nm. For example, the average diameter of the rubber particles can be in the range of about 25 to about 200 nm or about 50 to about 150 nm.

[0093] The rubber granules can be used in dry form or dispersed in a matrix, as described above.

[0094] Typically, the composition may contain about 5 to about 35% by weight of rubber particles.

[0095] In this invention, it is advantageous to use combinations of different rubber particles. The rubber particles can be different, for example, in terms of particle size, glass transition temperature of their respective materials, whether the materials are functionalized, the degree of functionalization and the mode of functionalization, and whether and how the surface is treated.

[0096] The rubber granules suitable for use in this invention are commercially available. For example, rubber granules supplied by Eliokem, such as NEP R0401 and NEP R401S (both based on acrylonitrile / butadiene copolymers); NEP R0501 (based on carboxylated acrylonitrile / butadiene copolymer; CAS No.: 9010-81-5); NEP R0601A (based on hydroxyl-terminated polydimethylsiloxane; CAS No.: 70131-67-8); and NEP R0701 and NEP R0701S (based on butadiene / styrene / 2-vinylpyridine copolymer; CAS No.: 25053-48-9), can be used. There are also those purchased under the brand name PARALOID, such as PARALOID 2314, PARALOID 2300, and PARALOID 2600, from Dow Chemical Co., Philadelphia, Pennsylvania, and those purchased under the brand name STAPHYLOID, such as STAPHYLOID AC-3832, from Ganz Chemical Co., Ltd., Osaka, Japan.

[0097] Rubber particles whose outer surface has been modified by treatment with reactive gases or other reagents, such as by forming polar groups (e.g., hydroxyl, carboxylic acid groups) on the particle surface, are also applicable herein. Exemplary reactive gases include, for example, ozone, Cl2, F2, O2, SO3, and oxidizing gases. Methods for surface modification of rubber particles using such reagents are known in the art and are described, for example, in U.S. Patent Nos. 5,382,635, 5,506,283, 5,693,714, and 5,969,053, all of which are incorporated herein by reference in their entirety. Suitable surface-modified rubber particles are also available commercially, such as rubber sold by Exousia Corporation under the trade name VISTAMER.

[0098] If the rubber granules are initially supplied in dry form, it is advantageous to ensure that these granules are adequately dispersed in the adhesive composition before curing. That is, it is best to break up the agglomerates of rubber granules to provide discrete individual rubber granules, which can be achieved by tightly and thoroughly mixing the dry rubber granules with the other components of the adhesive composition.

[0099] Thickeners may also be useful.

[0100] Stabilizers and inhibitors can also be used to control and prevent premature decomposition and polymerization of peroxides. Inhibitors can be selected from hydroquinone, benzoquinone, naphthoquinone, phenanthrenequinone, anthraquinone, and their substituted compounds. Various phenols can also be used as inhibitors, such as 2,6-di-tert-butyl-4-methylphenol. The amount of inhibitor used is from about 0.1% to about 1.0% of the total composition weight, without adversely affecting the curing rate of the polymerizable adhesive composition.

[0101] At least one of the first or second parts may also include pK a About 12 or smaller organic acids, such as sulfonamides, sulfonamides, citric acid, maleic acid, succinic acid, phthalic acid, dicarboxylic acid, maleic anhydride, maleic dianhydride, succinic anhydride, and phthalic anhydride.

[0102] In practical applications, the A and B components are each placed in separate containers within the device before use. During use, both components are extruded from their containers, mixed, and applied to the substrate surface. The container can be a dual-chamber structure, with the two components propelled into the chamber through orifices (which can be shared or adjacent) by a plunger, and then dispensed via a mixing nozzle. Alternatively, the container can be a coaxial or side-by-side bag-like container that can be cut or torn open to mix its contents and apply them to the substrate surface.

[0103] The invention can be more easily understood by reading the following embodiments. Example method

[0104] In summary, the bonding of the test components was performed as follows. Bonding was carried out using multiple methods: (a) application and curing on a worktable; (b) application and underwater curing on a worktable; (c) underwater application and curing on a worktable; and (d) underwater application and curing. All methods were performed at room temperature.

[0105] When partial or complete bonding is performed underwater, the components must be immersed in water, ensuring that water contacts all surfaces of the components. The components must be completely submerged in water. It is not necessary to remove the components from the water before applying the adhesive.

[0106] The adhesive was dispensed from the container and applied to the first part. The second part was overlapped by 0.5 inches (1.27 cm), and the two parts were then clamped together to allow the adhesive to cure, forming a bond between the parts. The time between dispensing from the container and overlapping the second part is the open time. Both adhesive application and curing were performed underwater. When testing the dry parts, the parts were not placed underwater. Both the adhesive application and curing were performed on dry parts, meaning there was no moisture on the surface.

[0107] The following substrates were tested: stainless steel, aluminum, low carbon steel, PC, PVC and ABS. result

[0108] Table 1 shows the tensile strengths obtained under different substrates and bonding conditions according to the methods described above (a)-(d). Table 1

[0109] The performance of the cartridges of the adhesives suitable for use in this invention was also examined after underwater storage (Tables 2 and 3). After 7 days of underwater storage, no signs of polymerization were found inside or around the cartridges, and the performance was not affected. Table 2 Table 3

[0110] Performance tests were also conducted on the nuts and bolts bonded according to the present invention. The substrate was prepared as described above. The results are listed in Table 4. Table 4

[0111] The tensile strength of metal-to-metal lap joints was measured in accordance with ASTM D1002-10 (2019), and the tensile strength of plastic-to-plastic lap joints was measured in accordance with ASTM D3163-01 (2023).

[0112] The stainless steel bolts have a major diameter of 9.968 to 9.732 mm, a minor diameter of 8.619 to 8.272 mm, and a pitch circle diameter of 8.994 to 8.862 mm. The stainless steel nuts have a thickness of 7.64 to 8.00 mm, a width of 16.73 to 17.00 mm, a minimum major diameter of 10.0 mm, a minor diameter of 8.376 to 8.676 mm, and a pitch circle diameter of 9.026 to 9.206 mm.

[0113] BOMS refers to black oxide low-carbon steel. The low-carbon steel bolts are coated with black oxide. The low-carbon steel nuts used are not coated with black oxide. The torque values ​​in the last two columns of Table 4 are the breaking torque (or fracture torque) and the preload torque (or pull-out torque), respectively, all measured according to ASTM D5649-15 standard (titled "Torque Strength of Adhesives for Threaded Fasteners").

[0114] Black oxide low-carbon steel bolts have a major diameter of 9.96 to 9.73 mm, a minor diameter of 8.08 to 7.98 mm, and a pitch circle diameter of 8.99 to 8.86 mm. Low-carbon steel nuts have a thickness of 8 ± 0.2 mm, a width of 14.0 to 14.3 mm, a minimum major diameter of 10.0 mm, a minor diameter of 8.38 to 8.28 mm, and a pitch circle diameter of 9.20 to 9.03 mm.

[0115] When the terms “comprising” and “having / including” are used herein with reference to this invention, they are used to specify the presence of the said feature, integer, step or component, but do not exclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

[0116] It should be understood that, for clarity, certain features of the invention have been described in separate embodiments, and these features may also be provided in combination in one embodiment. Conversely, for brevity, various features of the invention have been described in separate embodiments, and these features may also be provided individually or in any suitable sub-combination.

Claims

1. A method for bonding an underwater substrate, comprising: (a) Applying a cyanoacrylate composition to at least one substrate underwater, wherein the cyanoacrylate composition comprises: i. A first portion, the first portion comprising a cyanoacrylate component and a peroxide catalyst; and ii. The second part, comprising a free radical curable component and a transition metal, When mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component. (b) Curing the composition underwater.

2. The method according to claim 1, wherein the cyanoacrylate component comprises H2C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl.

3. The method according to any one of the preceding claims, wherein the peroxide catalyst comprises perbenzoate.

4. The method according to any one of the preceding claims, wherein the peroxide catalyst is tert-butyl perbenzoate.

5. The method according to any one of the preceding claims, wherein at least one of the first portion or the second portion further comprises a member selected from: pK a It is an organic acid of about 12 or less, such as sulfonamide, sulfonamide, citric acid, maleic acid, succinic acid, phthalic acid, dicarboxylic acid, maleic anhydride, maleic dianhydride, succinic anhydride and phthalic anhydride, or combinations thereof.

6. The method according to any one of the preceding claims, wherein the content of the peroxide catalyst is from about 0.01% by weight to about 10% by weight of the cyanoacrylate component.

7. The method according to any one of the preceding claims, wherein the free radical curable component of the composition is selected from (meth)acrylate components, compounds containing maleimide, itacamide or nadiimide, and combinations thereof.

8. The method according to any one of the preceding claims, wherein the free radical curable component of the composition is selected from the following (meth)acrylate components: polyethylene glycol di(meth)acrylate, tetrahydrofuran (meth)acrylate and di(meth)acrylate, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, benzyl methacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di(pentanediol) dimethacrylate, tetraethylene glycol dimethacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylenedimethacrylate, neopentanediol dimethacrylate, trimethylolpropane triacrylate, and bisphenol A mono(meth)acrylate and bisphenol A bis(meth)acrylate.

9. The method according to any one of the preceding claims, wherein the transition metal of the composition comprises a member selected from the group consisting of copper, vanadium, cobalt and iron.

10. The method according to any one of the preceding claims, wherein, The first portion of the composition is contained in the first chamber of the dual-chamber syringe, and the second portion of the composition is contained in the second chamber of the dual-chamber syringe.

11. The method according to any one of the preceding claims, wherein the second portion of the composition further comprises at least one of a plasticizer and a filler.

12. The method according to any one of the preceding claims, wherein the second part of the composition further comprises a toughening agent, optionally the toughening agent being selected from the group consisting of: (a) a reaction product of a combination of ethylene, methyl acrylate and a monomer having a carboxylic acid curing site; (b) a dimer of ethylene and methyl acrylate; (c) a combination of (a) and (b); (4) a vinylidene chloride-acrylonitrile copolymer; (5) a vinyl chloride / vinyl acetate copolymer; (6) a copolymer of polyethylene and polyvinyl acetate; and combinations thereof.

13. The method according to any one of the preceding claims, wherein the volume ratio of the first portion of the composition to the second portion of the composition is about 1:

1.

14. The method according to any one of the preceding claims, wherein the first portion of the composition and the second portion of the composition are each contained in a separate chamber of a dual-chamber container.

15. The method according to any one of the preceding claims, wherein at least one of the first portion or the second portion of the composition further comprises a member selected from: sulfonamide, sulfonamide, citric acid, maleic acid, succinic acid, phthalic acid, dicarboxylic acid, maleic anhydride, maleic dianhydride, succinic anhydride, phthalic anhydride, and combinations thereof.

16. The method according to any one of the preceding claims, wherein the free radical curable component is selected from the following (meth)acrylate components: ethoxylated bisphenol-A (meth)acrylate, ethoxylated bisphenol-F (meth)acrylate, methacrylate-functionalized polyurethane, and combinations thereof.

17. The method according to any one of the preceding claims, wherein the transition metal comprises copper selected from the following forms: copper(II) hydrate of 3,5-diisopropylsalicylate, copper(2,2,6,6-tetramethyl-3,5-heptadecyl)copper, copper(II) basic phosphate, copper(II) chloride, copper(II) acetate monohydrate, copper(II) tetra(acetonitrile)hexafluorophosphate (I), copper(II) formate hydrate, copper(II) tetraacetonitrile trifluoromethanesulfonate (I), copper(II) tetrafluoroborate, copper(II) perchlorate, copper(II) tetra(acetonitrile)tetrafluoroborate (I), copper(II) hydroxide, copper(II) hexafluoroacetylacetonate (II) hydrate, and copper(II) carbonate.

18. The method according to any one of the preceding claims, comprising exposing the composition to water for up to 45 seconds before bonding the surface of the second substrate to the coated surface of the first substrate.

19. The method according to any one of the preceding claims, wherein one or both substrates are metal, for example, one or both substrates are steel.

20. The method according to any one of the preceding claims, wherein one or both substrates are plastic materials.

21. Use of a cyanoacrylate composition for use as an underwater adhesive substrate, wherein the composition comprises: i. A first portion comprising a cyanoacrylate component and tert-butyl perbenzoate as a peroxide catalyst, said tert-butyl perbenzoate being present in an amount of about 0.01% by weight to about 10% by weight of the cyanoacrylate component; and ii. The second part, comprising a free radical curable component and a transition metal, The cyanoacrylate component comprises H2C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl, and wherein when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component.

22. An assembly comprising two underwater substrates bonded together by a cyanoacrylate composition, said cyanoacrylate composition comprising: i. A first portion comprising a cyanoacrylate component and tert-butyl perbenzoate as a peroxide catalyst, said tert-butyl perbenzoate being present in an amount of about 0.01% by weight to about 10% by weight of the cyanoacrylate component; and ii. The second part, comprising a free radical curable component and a transition metal, The cyanoacrylate component comprises H2C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl, and wherein when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component.

23. The component of claim 22, wherein one or both substrates are metal.

24. The component of claim 22, wherein one or both substrates are plastic materials.

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