How to glue underwater

Abstract

A method for bonding substrates underwater, comprising the steps of applying a cyanoacrylate composition to at least one substrate under water and curing the composition under water.

Description

[Technical field]

[0001] The present invention provides a method for underwater bonding with a curable cyanoacrylate composition. [Background technology]

[0002] <Brief Description of Related Art> Curable compositions such as cyanoacrylate adhesives are widely recognized for their excellent ability to rapidly bond a wide range of substrates, generally within a matter of minutes, and often within a matter of seconds depending on the particular 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, 27, 463-77, I. Skeist (ed.), Van Nostrand Reinhold, New York, 3rd ed. (1990). See also GH Millet, "Cyanoacrylate Adhesives," in Structural Adhesives: Chemistry and Technology, SR Hartshorn (ed.), Plenum Press, New York, pp. 249-307 (1986).

[0004] Cyanoacrylate adhesive compositions are suitable for curing in air. Advantageously, these compositions reach handling strength in seconds when cured in air and achieve greater than 60% strength within one minute when cured in air.

[0005] The polymerization of cyanoacrylates is initiated by nucleophiles that are present on most surfaces under normal atmospheric conditions. Initiation by surface chemistry means that sufficient initiating species are available when two surfaces are in intimate contact with a small layer of cyanoacrylate between the two surfaces. Under these conditions, strong adhesion can be achieved in a short time. Thus, in essence, cyanoacrylates often function as instant adhesives.

[0006] Cyanoacrylate adhesive compositions are not traditionally used for underwater applications because they are difficult to dispense underwater. It will be understood that underwater means that the substrates to be joined are completely submerged in water. The water is in contact with the substrate. Underwater, as used herein, does not refer to a substrate being underwater but not in contact with water. For example, underwater does not mean that the substrate is contained in a waterproof container and the container is in contact with water while the substrate is not in contact with water because it is kept dry by the waterproof container. In particular, the present invention relates to a method of using a cyanoacrylate adhesive dispensed from a container underwater. In such a case, the cyanoacrylate adhesive is dispensed through the water and onto the substrate surface, which is also in contact with water.

[0007] Dispensing a cyanoacrylate adhesive composition in water can cause the composition to react with the water and prematurely cure before it is applied to the substrate to which it is to be bonded. Indeed, cyanoacrylate compositions are well known to be sensitive to water, and in some cases, even trace amounts of water can cause premature curing, for example while stored for later use.

[0008] The performance, especially the durability, of cyanoacrylate adhesives is often questionable when exposed to water. Bonds formed using cured cyanoacrylate compositions may be susceptible to water. For example, exposure to water of the cured cyanoacrylate composition may cause the formed bond to eventually fail due to degradation over time. Generally, exposure to water reduces adhesive strength over time.

[0009] The cyanoacrylate adhesive composition, when dispensed in water, may be applied to a first substrate and partially cured before being bonded to a second substrate, in which case it may be possible to form a bond between the substrates, but the bond will be weaker because the composition has been partially cured before the substrates are bonded.

[0010] To overcome these problems, cyanoacrylate adhesive compositions are typically applied to substrates in air and the bonded substrates are then sometimes placed in water.

[0011] Underwater bonding using cyanoacrylate adhesive compositions would be advantageous in applications where the properties of cyanoacrylate adhesive compositions are beneficial. In situations where it is difficult to remove a substrate from water, it would be beneficial to dispense and cure the cyanoacrylate adhesive composition underwater. For example, when repairing or maintaining a boat, or installing a new part, such as a sensor, on a boat, it would be beneficial to use a cyanoacrylate adhesive composition to bond parts of a boat that are underwater, since it would eliminate the need to remove the boat from the water, which can be difficult and expensive and require the vessel to be returned to land. Similarly, it would be useful to be able to perform maintenance or repairs underwater, or to be able to attach parts to structures that are fully or partially underwater, such as oil rigs, bridges, pipelines, etc.

[0012] Coral reefs are formed by colonies of coral polyps. The skeleton of the coral polyp is formed from calcium carbonate, and the coral polyps are bound together by their calcium carbonate skeleton. Most of the coral reefs are formed by stony coral polyps (also called Scleractinia). Stony corals secrete a hard calcium carbonate exoskeleton that protects and supports the reef. Coral reefs can be damaged, for example, by excess nutrients or ocean acidification. Coral transplantation is considered an effective method to help coral reefs recover from damage. Healthy coral polyps are transplanted from healthy reefs to damaged reefs. The healthy polyps can help repair the reef. The transplanted coral polyps are fixed in their new location using cement or epoxy. If the transplanted coral polyp becomes dislodged from the transplanted location, the coral polyp will die and the transplant will not be successful. These methods can take a long time to dispense, apply, and cure the epoxy. This means that the user (often a diver) must spend long periods of time underwater, which can be expensive and dangerous.

[0013] Dizon et al. compared the use of a cyanoacrylate adhesive gel composition, an epoxy putty, and a marine epoxy to determine suitability for attaching coral polyps. Dizon et al. applied the cyanoacrylate adhesive composition on water and then submerged the coral polyps in water. Dizon et al. found that the cyanoacrylate adhesive composition was the easiest to handle, but was rated poorly in the important areas of adhesive effectiveness and transplant self-attachment.

[0014] It would be beneficial to provide an adhesive composition that has the advantages of cyanoacrylate compositions and is effective for adhering coral polyps during transplantation.

[0015] It would be beneficial to provide an alternative adhesive that: (1) can be dispensed while submerged in water, (2) can remain uncured for a sufficient period of time to allow application to the substrate to be bonded, (3) can be subsequently cured, desirably with a short cure time, (4) can develop a high strength bond, and (5) can retain bond strength. All of the above needs to be accomplished underwater. Summary of the Invention

[0016] In one aspect, the present invention provides a method for bonding underwater substrates, comprising the steps of: applying a cyanoacrylate composition to at least one substrate in water, the cyanoacrylate composition comprising: A first part, Contains a cyanoacrylate component and a rubber toughening agent; The rubber toughening agent comprises a first part comprising: (i) a reaction product of a combination of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site; (ii) a dipolymer of ethylene and methyl acrylate; or a combination of (i) and (ii); A second part, 2-Substituted benzothiazole or derivative thereof, where the 2-substituent is C 1-20 Alkyl group, C 2-20 Alkene group, C 8-20 Alkylbenzyl group, C 1-20 Alkylamino group, C 1-20 Alkoxy group, C 1-20 Alkylhydroxy group, ether group, sulfenamide group, C 1-20 Thioalkyl group or C 1-20 a second part comprising a thioalkoxy group; Including, At least one of the first part or the second part is a component comprising at least two (meth)acrylate functional groups; at least one benzonitrile compound substituted with at least two or more electron-withdrawing groups selected from halo, -NO2, or -CN, and combinations thereof; and At least one anhydrous component and curing the composition in water; The present invention provides a method comprising:

[0017] By underwater, it is meant that the substrate is submerged in water and the water contacts the substrate as the composition is applied. The substrate is not, for example, in a waterproof container to prevent direct exposure to water. Advantageously, this method allows for underwater bonding, an application that was previously precluded by the inability to remove and dry the assembly before bonding.

[0018] Advantageously, compositions applied in this manner can be dispensed submerged in water, remain uncured long enough to be applied to the substrates to be joined, and then cure in a short cure time. Advantageously, the cured composition cured in water develops high strength adhesion and retains that adhesive strength over time. The composition has a sufficiently long open time so that it can be dispensed, applied, and substrates joined before the composition cures, but desirably has a shorter cure time than compositions used in conventional methods to minimize the time the user must spend underwater.

[0019] The perceived shortcomings of cyanoacrylate compositions for bonding underwater substrates may be overcome by the cyanoacrylate hybrid compositions disclosed herein. All of the desirable properties of the present invention refer to the properties of the composition in an underwater environment. The composition of the present invention remains in place once dispensed. The composition of the present method may be dispensed in water, e.g., upon initial contact with water, there is no premature hardening that would prevent the composition from being dispensed onto a substrate. The composition of the present method must have a suitable viscosity to be dispensed. The composition may have a suitable buoyancy. For example, the composition of the present method is suitable not to be displaced by the forces caused by normal water flow.

[0020] The composition may be dispensed in water and used in a method of bonding underwater substrates. Without wishing to be bound by theory, it is believed that the combination of the cure rate control by the acrylate portion of the component containing at least two (meth)acrylate functional groups and the inherent high viscosity of the material results in this unexpected open time in aqueous environments. The first part of the composition may have a Casson viscosity of 200-600 mPa·s. The second part may have a viscosity of 1-20 mPa·s measured according to BS5350 part B8.

[0021] The cyanoacrylate component of the cyanoacrylate composition applied in the present method has the structure H2C=C(CN)-COOR, where R is C 1-15 Alkyl, C 2-15 Alkoxyalkyl groups, C 3-15 Cycloalkyl groups, C 2-15 Alkenyl group, C 6-15 Aralkyl group, C 5-15 Aryl group, C 3-15 Allyl groups and C 1-15 haloalkyl groups), for example, the cyanoacrylate component includes ethyl-2-cyanoacrylate.

[0022] The 2-substituted benzothiazole of the cyanoacrylate composition comprises at least one halo, C 1-20 Thioalkyl, C 1-20 Haloalkyl, C 1-20 Alkyl, C 1-20 It may be further substituted with alkoxy or hydroxyl substituents.

[0023] The halo substituents of the cyanoacrylate composition can be Cl, F, or Br.

[0024] The 2-substituted benzothiazoles of the cyanoacrylate composition are 5-chloro-2-methylbenzothiazole, 5-bromo-2-methyl-1,3-benzothiazole, 2-[(tert-butylamino)thio]-1,3-benzothiazole-5-ol, 5,6-dichloro-2-methyl-1,3-benzothiazole, 6-bromo-2-methyl-1,3-benzothiazole, 5-fluoro-2-methyl-1,3-benzothiazole, 6,7-dichloro-2-methyl-1,3-benzothiazole, 2,5-dimethyl-1,3-benzothiazole, 4,5,6 ,7-tetrafluoro-2-methyl-1,3-benzothiazole, 4,5,6,7-tetrafluoro-2-methyl-1,3-benzothiazole, 2-(allyloxy)-1,3-benzothiazole, 2-methyl-5-(methylthio)-1,3-benzothiazole, 2-(ethylthio)-1,3-benzothiazole, 2-(hexyloxy)-1,3-benzothiazole, 2-(1,3-dimethylbutoxy)-1,3-benzothiazole, 2-(octadecylthio)benzothiazole, 2-(1-ethylbutoxy)-1,3-benzothiazole, 2- (octyloxy)-1,3-benzothiazole, 2-(1-methylbutoxy)-1,3-benzothiazole, 2-(2-phenylethoxy)-1,3-benzothiazole, 2-[(1-methylheptyl)oxy]-1,3-benzothiazole, 2-allyl-1,3-benzothiazole, 2-[(1-methylhexyl)oxy]-1,3-benzothiazole, 4-chloro-2-methoxy-1,3-benzothiazole, 2-(3-methylbutoxy)-1,3-benzothiazole, 4-chloro-2-(ethynyloxy)-1,3-benzothiazole, 2,5,6-trimethyl-1,3-benzothiazole, 4-methoxy-2,7-dimethyl-1,3-benzothiazole, 5,6-dimethoxy-2-methyl-1,3-benzothiazole, 2,5,7-trimethyl-1,3-benzothiazole, 2-(butylthio)-1,3-benzothiazole, 5-chloro-2-(ethylthio)-1,3-benzothiazole, 2-methyl-1,3-benzothiazole, 2-(undecylthio)-1,3-benzothiazole, 2-methyl-1,3-benzothiazole, 5-methoxy-2-methylbenzothiazole, 2,The 2-substituted benzothiazole may be selected from the group consisting of 5-dimethylbenzothiazole, 6-methoxy-2-methylbenzothiazole, 2-methyl-5-benzothiazolol, 2-(methylmercapto)-benzothiazole, and 2-[(cyclohexylamino)thio]-benzothiazole), and preferably the 2-substituted benzothiazole is selected from the group consisting of 5-chloro-2-methylbenzothiazole, 2-methyl-1,3-benzothiazole, 2-(methylmercapto)-benzothiazole, 5-methoxy-2-methylbenzothiazole, 6-methoxybenzothiazole, 2,5-dimethylbenzothiazole, and 2-methyl-5-benzothiazolol.

[0025] The component of the cyanoacrylate composition that contains at least two (meth)acrylate functional groups has the formula:

[0026] [ka] wherein A is a C4-C alkoxy group that may optionally contain heteroatoms selected from the group consisting of O, N, and S. 30 is an aliphatic chain; The chains may include one or more acrylate or methacrylate functional groups and / or one or more C1-C 10 optionally substituted with an alkyl group; and R 1 and R 2 may be the same or different and are each arbitrarily selected from the group consisting of H and C1-C6 alkyl. It may be expressed as:

[0027] The component containing at least two (meth)acrylate functional groups of the cyanoacrylate composition may be selected from the group consisting of hexanediol diacrylate, hexanediol dimethacrylate, and di-trimethylolpropane tetraacrylate, and combinations thereof.

[0028] The component of the cyanoacrylate composition that contains at least two (meth)acrylate functional groups may be present in the second part (b).

[0029] The anhydride component of the cyanoacrylate composition may be selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, itaconic anhydride, diphenic anhydride, phenylsuccinic anhydride, 1,8-naphthalic anhydride, bromomaleic anhydride, 2,3-dichloromaleic anhydride, 2-dodecen-1-yl-succinic anhydride, homophthalic anhydride, tetrabromophthalic anhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-fluorophthalic anhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 3-nitrophthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride. , methacrylic anhydride, citraconic anhydride, hexahydro-4-methylphthalic anhydride, maleic anhydride, 2,3-diphenylmaleic anhydride, hexafluoroglutaric anhydride, 2,3-dimethylmaleic anhydride, tetrafluorophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride, bromomaleic anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, di-O-acetyl-L-tartaric anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride and combinations thereof.

[0030] The benzonitrile compound of the cyanoacrylate composition may be selected from the group consisting of tetrafluoroisophthalonitrile, 3,5-dinitrobenzonitrile; 2-chloro-3,5-dinitrobenzonitrile; pentafluorobenzonitrile; α,α,α-2-tetrafluoro-p-tolunitrile; and tetrachloroterephthalonitrile, and combinations thereof.

[0031] The benzonitrile compound of the cyanoacrylate composition may be present in an amount of from 0.05 to 5% by weight, preferably from 0.1 to 1% by weight, based on the total weight of the composition.

[0032] The anhydride component of the cyanoacrylate composition may be present in an amount of from 0.1 to 5 weight percent, preferably from 0.1 to 2 weight percent, based on the total weight of the composition.

[0033] The component containing at least two (meth)acrylate functional groups of the cyanoacrylate composition may be present in an amount of from 1 to 20 weight percent, preferably from 4 to 12 weight percent, based on the total weight of the composition.

[0034] The 2-substituted benzothiazole of the cyanoacrylate composition may be 5-chloro-2-methylbenzothiazole, the anhydride may be selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride or 4-methylphthalic anhydride and combinations thereof, and the at least one benzonitrile compound may be selected from the group consisting of tetrafluoroisophthalonitrile or pentafluorobenzonitrile and combinations thereof.

[0035] The benzonitrile of the cyanoacrylate composition may be present in an amount of 0.1 to 1 weight percent, the anhydride may be present in an amount of 0.1 to 2 weight percent, and the component containing at least two (meth)acrylate functional groups may be present in an amount of 4 to 12 weight percent, based on the total weight of the composition.

[0036] The cyanoacrylate composition optionally further comprises an accelerator component, which may be selected from the group consisting of calixarenes, oxacalixarenes, silacrowns, cyclodextrins, crown ethers, poly(ethylene glycol) di(meth)acrylates, ethoxylated hydroxy compounds, and combinations thereof.

[0037] The accelerator component may include a calixarene that is tetrabutyltetra[2-ethoxy-2-oxoethoxy]calix-4-arene.

[0038] The accelerator components are 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, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphthyl-16-crown-5, 1,2-naphthyl-15-crown-5, 1,2 ... The crown ether may include a crown ether selected from the group consisting of 1,2-methyl-benzo-18-crown-5, 1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5,6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6, and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7, and combinations thereof.

[0039] The accelerator component may include a poly(ethylene glycol) di(meth)acrylate contained in the following structure:

[0040] [ka] (wherein n is greater than 3.)

[0041] The cyanoacrylate component may further include additives selected from the group consisting of impact resistance additives, thixotropic agents, thickeners, dyes, thermal degradation enhancers, and combinations thereof.

[0042] The impact additive may be citric acid.

[0043] The cyanoacrylate component may further comprise at least one additive selected from the group consisting of 2-sulfobenzoic anhydride, triethylene glycol di(p-toluenesulfonate), trifluoroethyl p-toluenesulfonate, dimethyldioxolen-4-ylmethyl p-toluenesulfonate, p-toluenesulfonic anhydride, methanesulfonic anhydride, 1,3-propylene sulfite, dioxathiolane dioxide, 1,8-naphthosultone, 1,3-propane sultone, 1,4-butene sultone, allyl phenyl sulfone, 4-fluorophenyl sulfone, dibenzothiophene sulfone, bis(4-fluorophenyl)sulfone, ethyl p-toluenesulfonate, trifluoromethanesulfonic anhydride, ethylene sulfite, and combinations thereof.

[0044] The additive may be selected from 1,8-naphthosultone and ethylene sulfite, and combinations thereof.

[0045] In another aspect, the present invention provides a method for bonding underwater substrates, comprising the steps of: applying a cyanoacrylate composition to at least one substrate in water, The cyanoacrylate composition comprises: a first part comprising a cyanoacrylate component and a rubber toughening agent, the rubber toughening agent comprising (i) a reaction product of a combination of ethylene, methyl acrylate and a monomer having a carboxylic acid cure site, (ii) a dipolymer of ethylene and methyl acrylate, or a combination of (i) and (ii); A second part, comprising 2-substituted benzothiazoles or derivatives thereof, wherein the 2-substituent is C 1-20 Alkyl group, C 2-20 Alkene group, C 8-20 Alkylbenzyl group, C 1-20 Alkylamino group, C 1-20 Alkoxy group, C 1-20 Alkylhydroxy group, ether group, sulfenamide group, C 1-20Thioalkyl group or C 1-20 a second part comprising a thioalkoxy group; Including, At least one of the first part or the second part further comprises an anhydride component; The second part is a component containing at least two (meth)acrylate functional groups, present in an amount of 1 to 20% by weight, preferably 4 to 12% by weight, based on the total weight of the composition; and At least one benzonitrile compound substituted with at least two or more electron withdrawing groups selected from halo, -NO2, or -CN, and combinations thereof. and curing the composition in water; The present invention relates to a method comprising the steps of:

[0046] The 2-substituted benzothiazole of the cyanoacrylate composition may be selected from the group consisting of 5-chloro-2-methylbenzothiazole, 2-methyl-1,3-benzothiazole, 2-(methylmercapto)-benzothiazole, 5-methoxy-2-methylbenzothiazole, 6-methoxybenzothiazole, 2,5-dimethylbenzothiazole and 2-methyl-5-benzothiazolol, and combinations thereof.

[0047] The anhydride component of the cyanoacrylate composition may be selected from the group consisting of tetrafluoroisophthalonitrile, 3,5-dinitrobenzonitrile; 2-chloro-3,5-dinitrobenzonitrile; pentafluorobenzonitrile; α,α,α-2-tetrafluoro-p-tolunitrile; and tetrachloroterephthalonitrile, and combinations thereof.

[0048] The component containing at least two (meth)acrylate functional groups of the cyanoacrylate composition may be selected from the group consisting of hexanediol diacrylate, hexanediol dimethacrylate, and di-trimethylolpropane tetraacrylate, and combinations thereof.

[0049] The cyanoacrylate composition may be applied in a ratio of the first part to the second part of the cyanoacrylate composition ranging from about 1:1 to about 10:1 (e.g., 2:1, or 3:1, or 4:1, or 5:1, or 6:1, or 7:1, or 8:1, or 9:1).

[0050] The cyanoacrylate composition may be applied in a first to second part ratio of about 10:1.

[0051] A component of the cyanoacrylate composition containing at least two (meth)acrylate functional groups may be used as a carrier material for at least one benzonitrile compound.

[0052] The method of joining substrates underwater may include exposing the composition to water for up to 45 seconds before joining the surface of the second substrate with 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, such as up to 60 seconds, such as up to 45 seconds. Advantageously, a good open time allows time for the substrates to be mated correctly before the composition cures. A good open time allows time for assembly so that the substrates can be assembled into an assembly in the correct alignment. The composition has a good open time and allows the nozzle (through which the composition is dispensed and applied) to be replaced underwater without the composition curing. The composition may form a film with a top layer of the film, but the majority does not cure and has a good open time.

[0053] In the method of joining substrates underwater, the composition does not mix with water or disperse in water, for example in the water column. The physical properties of the composition, for example viscosity, are such that it does not mix with water and remains where it is applied. The outermost layer of the composition can harden to form a film that prevents the majority of the composition from contacting water. In this regard, hardening throughout the composition can occur after the two substrates are brought together.

[0054] The method of bonding underwater substrates may include curing the composition, and after 5 minutes of curing, such as after 24 hours of curing, such as after 168 hours, the composition has a bond strength of at least 0.6 N / mm 2 For example, at least one substrate may include calcium carbonate, e.g., may be formed in whole or in part from calcium carbonate.

[0055] In a method for bonding underwater substrates, the composition is cured to provide a bond strength of at least 4 N / mm after 5 minutes of curing, e.g., after 24 hours of curing, e.g., after 168 hours of curing. 2 For example, when at least one of the substrates is formed from a metal, such as steel.

[0056] In the methods of the present invention, one or both substrates may be naturally occurring and / or artificial.

[0057] Naturally occurring substrates include coral substrates, such as coral reefs. Coral reefs are formed by colonies of coral polyps. Calcium carbonate substrates may be joined by the methods of the present invention. These substrates include coral substrates, such as calcium carbonate substrates including the calcium carbonate skeleton of a coral substrate. For example, the methods of the present invention may be used to repair damage to a coral formation and / or to add coral material to a coral formation.

[0058] In a method for joining underwater substrates, one or both substrates may be metallic, for example, one or both substrates may be steel.

[0059] In the method of joining underwater substrates, at least one substrate may comprise a material selected from the group including steel, aluminum, wood, fiberglass, building materials including aggregates, sand, concrete / cement materials including ferrocement, and fiber reinforced plastics.

[0060] Suitably, both substrates may independently comprise a material selected from the group including steel, aluminium, wood, fibreglass, building materials including aggregates, sand, concrete / cement materials including ferrocement, fibre reinforced plastics.

[0061] In the method of bonding substrates underwater, at least one substrate may be a watercraft, such as a boat or ship, or a portion thereof. The method may be used to install an item on the boat or ship (e.g., to install a sensor or install a replacement part) or to perform repairs on the boat or ship. Using the method of the invention, this can be done without having to return to land to remove the boat or ship from the water.

[0062] In the method of joining underwater substrates, at least one substrate may be a structure located underwater or a portion of a structure that extends underwater, such as a bridge, oil or gas rig, pipeline, dam, wind turbine, etc. Because such structures cannot be removed from the water, it would be advantageous to be able to install products such as accessories, sensors, replacement parts, and the like, or perform repairs underwater.

[0063] In a method of joining underwater substrates, one or both substrates may comprise, e.g., be formed wholly or partially from, calcium carbonate, e.g., one or both substrates are shells, e.g., one or both substrates are scleractinia shells.

[0064] In the method of bonding substrates underwater, the nozzle life may be at least 4 minutes, such as at least 5 minutes. The dispensing nozzle has good nozzle life because the composition does not harden prematurely and block the nozzle. This is surprising because compositions containing cyanoacrylates usually harden quickly when exposed to moisture, such as when underwater. Advantageously, the nozzle life is increased, and therefore more composition can be applied before the nozzle needs to be replaced.

[0065] The method of bonding underwater substrates may be carried out in water containing various amounts of salt and / or minerals. For example, the method may be carried out in distilled water or treated water such as a public water supply. For example, the method may be carried out in distilled water or treated water such as a public / water supply. The method may be carried out in fresh water such as a well, river or lake. The method may be carried out in salt water, e.g., seawater, e.g., water having a salinity of about 30 g / L to about 50 g / L.

[0066] The method of joining substrates in water may be carried out in water having a pH in the range of about 6 to about 9, for example, about 6.5 to about 8, or about 7.5 to about 8.5.

[0067] In another aspect, the invention relates to an assembly comprising two submerged substrates joined by the method of the invention.

[0068] Detailed Description A method for bonding underwater substrates includes applying underwater a cyanoacrylate composition, which is described in detail below.

[0069] The cyanoacrylate component of the present method includes at least one cyanoacrylate monomer that may be selected with a number of substituents, such as, for example, H2C=C(CN)-COOR, where R is C 1-15 Alkyl group, C 2-15 Alkoxyalkyl groups, C 3-15 Cycloalkyl groups, C 2-15 Alkenyl group, C 6-15 Aralkyl group, C5-15 Aryl group, C 2-15 An example of a cyanoacrylate monomer is one selected from the group consisting of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate (such as n-butyl-2-cyanoacrylate), octyl cyanoacrylate, allyl cyanoacrylate, β-methoxyethyl cyanoacrylate, and combinations thereof. A particularly preferred cyanoacrylate monomer is ethyl-2-cyanoacrylate.

[0070] The cyanoacrylate component may be included in the compositions of the present method in an amount ranging from about 50% to about 99.98% by weight of the total composition, with a range of about 70% to about 85% being preferred.

[0071] The rubber toughening component may be selected from one of several candidates. One such candidate is the reaction product of a combination of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site. For example, the rubber toughening component may be an ethylene acrylic acid elastomer available from DuPont™ under the VAMAC trade name, such as VAMAC N123, VAMAC B-124, etc. VAMAC N123 and VAMAC B-124 are reported by DuPont to be masterbatches of ethylene / acrylic elastomers. DuPont's material VAMAC G is a similar copolymer, but does not contain fillers or stabilizers to impart color. VAMAC VCS rubber appears to be the base rubber from which the remaining members of the VAMAC product line are compounded. VAMAC VCS (also known as VAMAC MR) is a reaction product of a combination of ethylene, methyl acrylate, and monomers with carboxylic acid cure sites which, once formed, is substantially free of processing aids such as mold release agents octadecylamine, complex organophosphate esters and / or stearic acid, and antioxidants such as substituted diphenylamines.

[0072] Recently, DuPont has offered rubbers made from ethylene and methyl acrylate under the trade names VAMAC VMX 1012 and VCD 6200. VAMAC VMX 1012 rubber is believed to have little or no carboxylic acid in the polymer backbone. Like VAMAC VCS rubber, VAMAC VMX 1012 and VCD 6200 rubber are substantially free of processing aids such as the above-mentioned mold release agent octadecylamine, complex organic phosphate esters and / or stearic acid, and antioxidants such as substituted diphenylamines. All of these VAMAC elastomeric polymers are useful herein.

[0073] In one variation, the reaction product thus formed is rendered substantially free of processing aids and antioxidants. The processing aids are mold release agents such as octadecylamine (reported by DuPont™ to be commercially available under the trade name ARMEEN 18D from Akzo Nobel), complex organophosphates (reported by DuPont™ to be commercially available under the trade name VANFRE VAM from RT Vanderbilt Co., Inc.), stearic acid and / or polyethylene glycol ether waxes. The antioxidants are substituted diphenylamines (reported by DuPont™ to be commercially available under the trade name NAUGARD® 445 from Uniroyal Chemical).

[0074] Alternatively, the rubber toughening component is a dipolymer of ethylene and methyl acrylate. In one variation of this option, the dipolymer so formed is rendered substantially free of processing aids and antioxidants. Of course, the rubber toughening agent may also be a combination of the reaction product of the previous paragraph and the dipolymer of this paragraph, either or both of which may be substantially free of processing aids and antioxidants.

[0075] The rubber toughening component may be present in a concentration of from about 1.5% to about 20% by weight, such as from about 5% to about 15% by weight, with from about 8% to about 10% by weight being particularly preferred, based on the total weight of the composition.

[0076] Advantageously, when the rubber toughening component is present in an amount of about 5% to about 15% by weight, based on the total weight of the composition, the compositions of the present invention have improved flexibility and toughness.

[0077] The component containing at least two (meth)acrylate functional groups may be an aliphatic compound having at least two (meth)acrylate functional groups, preferably at the end of the aliphatic chain, but also suitably pendant along the aliphatic chain, especially when there are more than two (meth)acrylate functional groups. Alkane di- and tri-ol di- and tri-(meth)acrylates, respectively, are some examples of such compounds. More specifically, hexanediol dimethacrylate and hexanediol diacrylate are preferred. Furthermore, di-trimethylolpropane tetraacrylate and trimethylolpropane trimethacrylate are also preferred.

[0078] For example, the component containing at least two (meth)acrylate functional groups may have the formula:

[0079] [ka] wherein A is a C4-C alkoxy group that may optionally contain heteroatoms selected from O, N and S. 30 an aliphatic chain, wherein the chain comprises one or more acrylate and / or methacrylate functional groups and / or one or more C1-C 10 is optionally substituted with an alkyl group, R 1 and R 2 may be the same or different and are each arbitrarily selected from H and C1-C6 alkyl).

[0080] Preferably, the component having at least two (meth)acrylate functional groups has the formula:

[0081] [ka] (Wherein, R1 and R 2 are the same or different and are selected from H or Me; X is a C4-C 30 an alkyl chain, wherein the chain comprises one or more acrylate and / or methacrylate functional groups, and / or one or more C1-C 10 Optionally substituted with an alkyl group.

[0082] X is C4~C 30 For example, X may be a C4 alkyl chain, or a C5 alkyl chain, or a C6 alkyl chain, or a C7 alkyl chain, or a C8 alkyl chain, or a C9 alkyl chain, or a C 10 Alkyl chain, or C 11 Alkyl chain, or C 12 It may be an alkyl chain. Suitably, X may be an alkyl chain selected from the group consisting of butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl chains.

[0083] Suitably, such ingredients impart improved thermal and humid ageing performance to the compositions of the present invention.

[0084] The component having at least two (meth)acrylate functional groups may be selected from:

[0085] [ka]

[0086] The component containing at least two (meth)acrylate functional groups may be present in a concentration of about 0.5 to about 20 wt%, for example about 1 to about 15 wt%, with about 4 to about 12 wt% being particularly desirable. When the component containing at least two (meth)acrylate functional groups is present in an amount greater than about 20 wt%, the tensile strength of the composition is reduced. When the component is present in an amount less than about 1 wt%, the improvement in wet aging is reduced. When this component is present in an amount of about 4 to about 12 wt%, the greatest improvement in wet aging while maintaining tensile strength performance is observed. Advantageously, the component containing at least two (meth)acrylate functional groups, in addition to acting as an active plasticizer and improving the wet aging performance of the two-part composition, can function as a carrier for the benzothiazole component, thereby eliminating the need to include an additional carrier.

[0087] The anhydride component may be aromatic, such as phthalic anhydride, or a fully or partially hydrogenated version thereof, although other anhydrides with or without phthalic anhydride (or a fully or partially hydrogenated version thereof) may also be used.

[0088] For example, the anhydride component may be phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, itaconic anhydride, diphenic anhydride, phenylsuccinic anhydride, 1,8-naphthalic anhydride, bromomaleic anhydride, 2,3-dichloromaleic anhydride, 2-dodecen-1-yl-succinic anhydride, homophthalic anhydride, tetrabromophthalic anhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-fluorophthalic anhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 3-nitrophthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, methacrylonitrile, tetrabromophthalic anhydride ... The anhydride component may be suitably selected from phthalic anhydride, citraconic anhydride, hexahydro-4-methylphthalic anhydride, maleic anhydride, 2,3-diphenylmaleic anhydride, hexafluoroglutaric anhydride, 2,3-dimethylmaleic anhydride, tetrafluorophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride, bromomaleic anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, di-O-acetyl-L-tartaric anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride and combinations thereof. Suitably, the anhydride component is phthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride or 4-methylphthalic anhydride.

[0089] The anhydride component may be present at a concentration of about 0.1 to about 5 wt.%, for example about 0.1 to about 2 wt.%, based on the total weight of the composition, with about 0.5 wt.% being particularly preferred. If the anhydride component is present at a concentration of more than about 5 wt.%, based on the total weight of the composition, no further improvement in performance is observed. If the anhydride component is present at less than 0.1 wt.%, based on the total weight of the composition, the improvement in wet aging performance is less significant.

[0090] Heat resistance agents may also be added, including certain sulfur-containing compounds such as sulfonates, sulfinates, sulfates, and sulfites, as described in U.S. Patent No. 5,328,944 (Attarwala), the disclosure of which is expressly incorporated herein by reference.

[0091] For example, the compositions of the present invention may optionally contain additives that impart heat resistance, such as 2-sulfobenzoic anhydride, triethylene glycol di(p-toluenesulfonate), trifluoroethyl p-toluenesulfonate, dimethyldioxolen-4-ylmethyl p-toluenesulfonate, p-toluenesulfonic anhydride, methanesulfonic anhydride, 1,3 propylene sulfite, dioxathiolane dioxide, 1,8-naphthosultone, 1,3-propane sultone, 1,4-butene sultone, allyl phenyl sulfone, 4-fluorophenyl sulfone, dibenzothiophene sulfone, bis(4-fluorophenyl)sulfone, ethyl p-toluenesulfonate, and trifluoromethanesulfonic anhydride.

[0092] The cyanoacrylate compositions of the present invention may also include accelerators such as any one or more selected from calixarenes and oxacalixarenes, silacrowns, crown ethers, cyclodextrins, poly(ethylene glycol) di(meth)acrylates, ethoxylated hydric compounds, and combinations thereof.

[0093] Many calixarenes and oxacalixarenes are known and have been reported in the patent literature, see, e.g., 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 each of which are expressly incorporated herein by reference.

[0094] For example, with respect to calixarenes, those within the following structure are useful herein:

[0095] [ka] (In the formula, R 1 is C 1-10 Alkyl, C 1-10 Alkoxy, Substituted C1-10 Alkyl or C 1-10 is a substituted alkoxy; R 2 is H or C 1-10 alkyl; n is 4, 6, or 8.

[0096] One particularly desirable calixarene is tetrabutyltetra[2-ethoxy-2-oxoethoxy]calix-4-arene.

[0097] Many crown ethers are known, including, for example, 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, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decaaryl-15-crown-4, 1,2-decaaryl-15-crown-5, 1,2-decaaryl-15-crown-6 ...5, 1,2-decaaryl-15-crown-6, 1,2-decaaryl-15-crown-5, 1,2-decaaryl-15-crown-5, 1,2-decaaryl-15-crown-6, 1,2 -crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphthyl-16-crown-5, 1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5,6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6, and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7. See U.S. Pat. No. 4,837,260 (Sato), the disclosure of which is expressly incorporated herein by reference.

[0098] Silacrowns are also widely known and have been reported in the literature. For example, a typical silacrown may be represented within the following structure:

[0099] [ka] (In the formula, R 3 and R 4 is an organic group that does not itself cause polymerization of the cyanoacrylate monomer, and R 5 is H or CH3, and n is an integer of 1 to 4. 3 Groups and R 4 Examples of groups include R groups, C groups such as methoxy, etc. 1-20 R is an alkoxy group, and an aryloxy group such as phenoxy.3 Groups and R 4 The group may contain halogen or other substituents, an example of which is trifluoropropyl. However, basic groups such as amino, substituted amino, and alkylamino may be R 4 Groups and R 5 Not suitable as a base.

[0100] Specific examples of silacrown compounds useful in the compositions of the present invention include the following:

[0101] [ka] Dimethylsila-11-crown-4;

[0102] [ka] Dimethylsila-14-crown-5;

[0103] [ka] and dimethylsila-17-crown-6. See, for example, US Pat. No. 4,906,317 (Liu), the disclosure of which is expressly incorporated herein by reference.

[0104] Many cyclodextrins may be used in conjunction with the present invention, for example, those described and claimed in U.S. Patent No. 5,312,864 (Wenz) (the disclosure of which is expressly incorporated herein by reference) as hydroxyl derivatives of α, β, or γ-cyclodextrin that are at least partially soluble in cyanoacrylates would be suitable choices.

[0105] For example, poly(ethylene glycol) di(meth)acrylates suitable for use herein include those within the following structure:

[0106] [ka] (wherein n is greater than 3, e.g., in the range of 3 to 12, with n being particularly preferred as 9). More specific examples include PEG200DMA (wherein n is about 4), PEG400DMA (wherein n is about 9), PEG600DMA (wherein n is about 14), and PEG800DMA (wherein n is about 19), where the number (e.g., 400) represents the average molecular weight of the glycol portion of the molecule excluding the two methacrylate groups, expressed as grams / mole (i.e., 400 g / mol). A particularly preferred PEG DMA is PEG400DMA.

[0107] Also, among the ethoxylated hydroxy compounds (or ethoxylated fatty alcohols that may be used), suitable ones may be selected from those contained in the following structure:

[0108] [ka] (In the formula, C m can be a linear or branched alkyl or alkenyl chain, m is an integer from 1 to 30, for example from 5 to 20, n is an integer from 2 to 30, for example from 5 to 15, R is H or alkyl, for example C 1-6 It may be alkyl.

[0109] Commercially available examples of materials included in the above structure include those offered under the DEHYDOL® trade name by BASF SE, Ludwigshafen, Germany.

[0110] When used, accelerators encompassed by the above structure may be included in the composition in an amount ranging from about 0.01% to about 10% by weight of the total composition, with a range of from about 0.1% to about 0.5% by weight being preferred, and about 0.4% by weight being particularly preferred.

[0111] Stabilizer packages are also usually included in cyanoacrylate compositions. Stabilizer packages may include one or more free radical stabilizers and anionic stabilizers, the types and amounts of which 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 each of which are incorporated herein by reference.

[0112] Commonly used free radical stabilizers include hydroquinone, while commonly used anionic stabilizers include boron trifluoride, boron trifluoride etherate, sulfur trioxide (and its hydrolysis products), sulfur dioxide, and methanesulfonic acid.

[0113] Other additives may be included to impart additional physical properties, such as improved impact resistance (e.g., citric acid), thickness (e.g., polymethyl methacrylate), thixotropy (e.g., fumed silica), color, etc.

[0114] These other additives may be used individually in the composition of the present invention in an amount of about 0.05% to about 20% by weight, for example about 1% to 15% by weight, preferably 5% to 10% by weight, depending of course on the type of additive. For example, more specifically, citric acid may be used in the composition of the present invention in an amount of 5 to 500 ppm, preferably 10 to 100 ppm.

[0115] A method for bonding substrates underwater includes applying a composition disclosed herein to at least one substrate underwater and allowing the composition to cure.

[0116] The nozzle life may be at least 4 minutes, such as at least 5 minutes. This means that the composition will not harden in this time in the nozzle used to dispense while the composition is being applied. A thin layer of the composition may harden at the tip of the nozzle where the composition comes into contact with water. The majority of the composition in the nozzle body that does not come into contact with water will remain unhardened. It will still be possible to dispense the composition from the nozzle because the composition has good nozzle life in water.

[0117] Advantageously, the composition may be exposed to water for up to 45 seconds before joining the surface of the second substrate with the coated surface of the first substrate, and the composition remains uncured and capable of forming a bond between the substrates.

[0118] The method includes curing the composition in water. The composition is not removed from the water to cure. Upon curing, the bond formed becomes strong. Upon curing, the bond formed maintains its strength over time, making the method of the present invention suitable for bonding substrates for long periods of time. The bond has a strength of at least 0.6 N / mm after 5 minutes of curing, such as after 24 hours of curing, such as after 168 hours. 2 The adhesive may have a shear strength (measured according to ASTM D1002) of at least 4 N / mm after 5 minutes of curing, e.g. after 24 hours of curing, e.g. after 168 hours. This adhesive strength may be achieved even with difficult to bond materials such as calcium carbonate. As calcium carbonate effectively bonds for long periods of time (e.g. 168 hours), the method is suitable for reef applications, e.g. for coral transplantation. The strength of the bond achieved may be greater than the breaking point of calcium carbonate, meaning that the calcium carbonate may break before the bond breaks. The bond may have a shear strength of at least 4 N / mm after 5 minutes of curing, e.g. after 24 hours of curing, e.g. after 168 hours. 2A substrate having a higher shear strength can achieve a higher shear strength bond because the substrate will not break before the bond breaks. For example, a metal, such as steel, for example grit blasted mild steel (GBMS), has a higher shear strength than the bond formed by the present method, and after 5 minutes cure, for example after 24 hours cure, for example after 168 hours, can have a shear strength of at least 4 N / mm 2 The composition may have a shear strength (measured in accordance with ASTM D1002) of 0.01 to 0.15 mm. EXAMPLES

[0119] Briefly, the parts to be tested were bonded as follows: The parts were submerged in water so that all surfaces of the parts were in contact with the water. The parts were completely submerged. The parts were not removed from the water before the adhesive was applied.

[0120] The components of a representative composition are shown in Table 1.

[0121] [Table 1]

[0122] The flexible CA component includes ethyl-2-cyanoacrylate, a rubber toughening agent including (i) a reaction product of a combination of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site, (ii) a dipolymer of ethylene and methyl acrylate, or a combination of (i) and (ii), and a stabilizer. The rubber toughening agent used can be any of those described herein, but in this example is that offered under the trade name VAMAC® VCS5500. The stabilizer used here is a combination of methanesulfonic acid and SO2. Based on the total weight of the flexible CA composition, the ethyl-2-cyanoacrylate is present at greater than 80% by weight and the rubber toughening agent is present at 6% by weight. In the composition of Table 1, the ratio of the first part (Part A) to the second part (Part B) is 10:1, but other ratios can be used.

[0123] The composition was dispensed from a container and applied to the first part. A second part was overlapped by 1 inch (2.54 cm) and the parts were clamped to allow the adhesive to cure and form a bond between the parts. The time between dispensing the composition from the container and overlapping the second part was referred to as the open time. Both the application of the adhesive and the adhesive curing were done underwater. For testing of dry parts, the parts were not placed underwater. The parts were dry and free of surface moisture when the adhesive was applied and when the adhesive cured. The shear strength of the bond was measured according to ASTM D1002.

[0124] The following substrates were tested: grit blasted mild steel (GBMS), calcium carbonate.

[0125] result GBMS parts were bonded with an open time of 0 seconds; that is, the composition was applied to the parts and the parts were bonded immediately. The parts were not removed from the water while the adhesive cured. The bond was cured while fully submerged in water. As shown in Table 2, the adhesive achieved good handling strength after curing for 5 minutes. The bond strength when the adhesive was applied and cured underwater is equivalent to the bond strength achieved with dry parts. This strength allows the bonded parts to be handled without the bond failing. The strength of the composition applied and cured underwater was equivalent to the strength achieved with the adhesive applied to dry parts. The bond strength was maintained after 24 hours of curing, as shown in Table 2. The bond strength was maintained after 168 hours of curing, as shown in Table 2.

[0126] GMBS parts were bonded with open times of 0 seconds (the composition was applied and the parts were bonded immediately), 30 seconds (the composition was applied and the parts were bonded after 30 seconds), and 45 seconds (the composition was applied and the parts were bonded after 45 seconds). The adhesive was applied under water, then the parts were removed from the water and cured in air for 24 hours. The adhesive formed a strong bond even after 45 seconds of exposure to water. As shown in Table 3, open times of 0, 30, and 45 seconds formed a strong bond after 24 hours.

[0127] The calcium carbonate parts were bonded with an open time of 0 seconds. The parts were not removed from the water while the adhesive cured. The bond was cured while fully submerged in water. As shown in Table 2, the adhesive achieved good handling strength after curing for 5 minutes. The bond strength achieved with the adhesive applied and cured underwater is comparable to that achieved with dry parts. The tensile strength of calcium carbonate is approximately 1 N / mm 2 Since the adhesive strength is so high, the parts can break without the bond failing. This strength allows the joined parts to be handled without the bond failing. The strength of the composition applied and cured in water was comparable to that achieved with the adhesive applied to dry parts. As shown in Table 2, the adhesive strength was maintained after 24 hours of curing. As shown in Table 2, the adhesive strength was maintained after 168 hours of curing.

[0128] Calcium carbonate parts were bonded with open times of 0 seconds (the composition was applied and the parts were bonded immediately), 30 seconds (the composition was applied and the parts were bonded after 30 seconds), and 45 seconds (the composition was applied and the parts were bonded after 45 seconds). The adhesive was applied in water, after which the parts were removed from the water and cured in air for 24 hours. The adhesive formed a strong bond even after 45 seconds of exposure to water. As shown in Table 3, open times of 0, 30, and 45 seconds produced strong bonds after 24 hours. The tensile strength of calcium carbonate is approximately 1 N / mm 2 Therefore, it is possible for the part to break without the bond being broken.

[0129] [Table 2]

[0130] [Table 3]

[0131] The nozzle life of a package of adhesive in water is greater than 5 minutes if the adhesive is dispensed every 2 minutes or less. Table 4 shows that the adhesive composition was easily dispensed and the nozzle did not clog after 5 minutes. The adhesive composition was easily extruded from the nozzle at 0 minutes, i.e., when the nozzle was first opened to the water. After 1 minute of opening to the water, the composition was easily extruded from the nozzle. The nozzle being in water did not prevent the composition from being dispensed. After another minute in water (2 minutes), the composition was easily dispensed from the nozzle. After another minute in water (3 minutes), the composition was easily dispensed from the nozzle. After another 2 minutes in water (5 minutes), the surface of the composition began to harden, so the tip of the nozzle had to be cleaned. The majority of the composition had not hardened, only a thin layer of the composition had begun to harden. The tip of the nozzle was cleaned to remove the hardened layer, and the composition was easily dispensed from the nozzle as the majority of the hardening had not occurred.

[0132] [Table 4]

[0133] As used herein in connection with the present invention, the terms "comprises / comprising" and "having / including" are used to specify the presence of stated features, integers, steps, or ingredients, but do not exclude the presence or addition of one or more other features, integers, steps, ingredients, or groups thereof.

[0134] It is appreciated that certain features of the invention that are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

Claims

1. 1. A method for joining submerged substrates, comprising: applying a cyanoacrylate composition to at least one substrate in water; the cyanoacrylate composition comprising: (a) a first part, Contains a cyanoacrylate component and a rubber toughening agent, The rubber toughening agent comprises a first part comprising: (i) a reaction product of a combination of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site; (ii) a dipolymer of ethylene and methyl acrylate; or a combination of (i) and (ii); (b) a second part, 2-substituted benzothiazoles or derivatives thereof (wherein the 2-substituent is C １－２０ Alkyl group, C ２－２０ Alkene group, C ８－２０ Alkylbenzyl group, C １－２０ Alkylamino group, C １－２０ Alkoxy group, C １－２０ Alkylhydroxy group, ether group, sulfenamide group, C １－２０ Thioalkyl group or C １－２０ a second part comprising a thioalkoxy group; Including, At least one of the first part or the second part is a component comprising at least two (meth)acrylate functional groups; Hello, -NO ２ at least one benzonitrile compound substituted with at least two or more electron-withdrawing groups selected from ——, ——, ——, ——, ——, or —CN and combinations thereof; and further comprising at least one anhydride component; curing the composition in water; A method comprising:

2. The cyanoacrylate component of the cyanoacrylate composition has the structure H ２ C=C(CN)-COOR (wherein R is C １－１５ Alkyl group, C ２－１５ Alkoxyalkyl group, C ３－１５ Cycloalkyl group, C ２－１５ Alkenyl group, C ６－１５ Aralkyl group, C ５－１５ Aryl group, C ３－１５ Allyl group and C １－１５ 2. The method of claim 1, wherein the cyanoacrylate component is selected from materials included in the group consisting of alkyl, aryl, methyl ...

3. The 2-substituted benzothiazole of the cyanoacrylate composition comprises at least one halo, C １－２０ Thioalkyl, C １－２０ Haloalkyl, C １－２０ Alkyl, C １－２０ 3. The method of claim 1 or 2, further substituted with alkoxy or hydroxyl substituents.

4. The method of claim 3 , wherein the halo substituent of the cyanoacrylate composition is Cl, F, or Br.

5. The 2-substituted benzothiazole of the cyanoacrylate composition is selected from the group consisting of 5-chloro-2-methylbenzothiazole, 5-bromo-2-methyl-1,3-benzothiazole, 2-[(tert-butylamino)thio]-1,3-benzothiazole-5-ol, 5,6-dichloro-2-methyl-1,3-benzothiazole, 6-bromo-2-methyl-1,3-benzothiazole, 5-fluoro-2-methyl-1,3-benzothiazole, 6,7-dichloro-2-methyl-1,3-benzothiazole, 2,5-dimethyl-1,3-benzothiazole, 4,5, 6,7-tetrafluoro-2-methyl-1,3-benzothiazole, 4,5,6,7-tetrafluoro-2-methyl-1,3-benzothiazole, 2-(allyloxy)-1,3-benzothiazole, 2-methyl-5-(methylthio)-1,3-benzothiazole, 2-(ethylthio)-1,3-benzothiazole, 2-(hexyloxy)-1,3-benzothiazole, 2-(1,3-dimethylbutoxy)-1,3-benzothiazole, 2-(octadecylthio)benzothiazole, 2-(1-ethylbutoxy)-1,3-benzothiazole, 2 -(octyloxy)-1,3-benzothiazole, 2-(1-methylbutoxy)-1,3-benzothiazole, 2-(2-phenylethoxy)-1,3-benzothiazole, 2-[(1-methylheptyl)oxy]-1,3-benzothiazole, 2-allyl-1,3-benzothiazole, 2-[(1-methylhexyl)oxy]-1,3-benzothiazole, 4-chloro-2-methoxy-1,3-benzothiazole, 2-(3-methylbutoxy)-1,3-benzothiazole, 4-chloro-2-(ethynyloxy)-1,3-benzothiazole, 2,5,6-trimethyl-1,3-benzothiazole, 4-methoxy-2,7-dimethyl-1,3-benzothiazole, 5,6-dimethoxy-2-methyl-1,3-benzothiazole, 2,5,7-trimethyl-1,3-benzothiazole, 2-(butylthio)-1,3-benzothiazole, 5-chloro-2-(ethylthio)-1,3-benzothiazole, 2-methyl-1,3-benzothiazole, 2-(undecylthio)-1,3-benzothiazole, 2-methyl-1,3-benzothiazole, 5-methoxy-2-methylbenzothiazole, 2,The method according to claim 1 or 2, wherein the 2-substituted benzothiazole is selected from the group consisting of 5-dimethylbenzothiazole, 6-methoxy-2-methylbenzothiazole, 2-methyl-5-benzothiazolol, 2-(methylmercapto)-benzothiazole, and 2-[(cyclohexylamino)thio]-benzothiazole, and preferably the 2-substituted benzothiazole is selected from the group consisting of 5-chloro-2-methylbenzothiazole, 2-methyl-1,3-benzothiazole, 2-(methylmercapto)-benzothiazole, 5-methoxy-2-methylbenzothiazole, 6-methoxybenzothiazole, 2,5-dimethylbenzothiazole, and 2-methyl-5-benzothiazolol.

6. The cyanoacrylate composition has a component containing at least two (meth)acrylate functional groups represented by the formula: 【Chemistry 1】 wherein A is a C which may optionally contain heteroatoms selected from the group consisting of O, N and S. ４ ~C ３０ is an aliphatic chain of The chain may contain one or more acrylate or methacrylate functional groups and / or one or more C １ ~C １０ optionally substituted with alkyl groups; and R １ and R ２ may be the same or different, and are H and C １ ~C ６ alkyl) The method according to claim 1 or 2, wherein

7. 3. The method of claim 1, wherein the component of the cyanoacrylate composition containing at least two (meth)acrylate functional groups is selected from the group consisting of hexanediol diacrylate, hexanediol dimethacrylate, and di-trimethylolpropane tetraacrylate, and combinations thereof.

8. 3. The method of claim 1 or 2, wherein the component of the cyanoacrylate composition containing at least two (meth)acrylate functional groups is present in the second part (b).

9. The anhydride component of the cyanoacrylate composition may be selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, itaconic anhydride, diphenic anhydride, phenylsuccinic anhydride, 1,8-naphthalic anhydride, bromomaleic anhydride, 2,3-dichloromaleic anhydride, 2-dodecen-1-yl-succinic anhydride, homophthalic anhydride, tetrabromophthalic anhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-fluorophthalic anhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 3-nitrophthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, methacrylate dianhydride, methyl phthalic anhydride, methyl ...

3. The method of claim 1, wherein the carboxylic acid anhydride is selected from the group consisting of carboxylic acid anhydride, citraconic anhydride, hexahydro-4-methylphthalic anhydride, maleic anhydride, 2,3-diphenylmaleic anhydride, hexafluoroglutaric anhydride, 2,3-dimethylmaleic anhydride, tetrafluorophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride, bromomaleic anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, di-O-acetyl-L-tartaric anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, and combinations thereof.

10. 3. The method of claim 1 or 2, wherein the benzonitrile compound of the cyanoacrylate composition is selected from the group consisting of tetrafluoroisophthalonitrile, 3,5-dinitrobenzonitrile; 2-chloro-3,5-dinitrobenzonitrile; pentafluorobenzonitrile; α,α,α-2-tetrafluoro-p-tolunitrile; and tetrachloroterephthalonitrile, and combinations thereof.

11. 3. The method of claim 1, wherein the benzonitrile compound of the cyanoacrylate composition is present in an amount of 0.05 to 5 wt. %, preferably 0.1 to 1 wt. %, based on the total weight of the composition.

12. The method of claim 1 or 2, wherein the anhydride component of the cyanoacrylate composition is present in an amount of 0.1 to 5 wt. %, preferably 0.1 to 2 wt. %, based on the total weight of the composition.

13. 3. The method of claim 1 or 2, wherein the component comprising at least two (meth)acrylate functional groups of the cyanoacrylate composition is present in an amount of 1 to 20 wt%, preferably 4 to 12 wt%, based on the total weight of the composition.

14. 3. The method of claim 1 or 2, wherein the 2-substituted benzothiazole of the cyanoacrylate composition is 5-chloro-2-methylbenzothiazole, the anhydride is selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, or 4-methylphthalic anhydride, and combinations thereof, and the at least one benzonitrile compound is selected from the group consisting of tetrafluoroisophthalonitrile or pentafluorobenzonitrile, and combinations thereof.

15. 15. The method of claim 14, wherein the benzonitrile of the cyanoacrylate composition is present in an amount of 0.1 to 1 weight percent, the anhydride is present in an amount of 0.1 to 2 weight percent, and the component comprising at least two (meth)acrylate functional groups is present in an amount of 4 to 12 weight percent, based on the total weight of the composition.

16. 3. The method of claim 1 or 2, wherein the cyanoacrylate composition further comprises an accelerator component selected from the group consisting of calixarenes, oxacalixarenes, silacrowns, cyclodextrins, crown ethers, poly(ethylene glycol) di(meth)acrylates, ethoxylated hydroxy compounds, and combinations thereof.

17. 17. The method of claim 16, wherein the promoter component comprises a calixarene that is tetrabutyltetra[2-ethoxy-2-oxoethoxy]calix-4-arene.

18. The accelerator component is selected from the group consisting of 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, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphthyl-16-crown- 17. The method of claim 16, wherein the crown ether comprises a crown ether selected from the group consisting of 1,5,1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5,6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6, and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7, and combinations thereof.

19. 17. The method of claim 16, wherein the accelerator component comprises a poly(ethylene glycol) di(meth)acrylate having the following structure: 【Chemistry 2】 where n is greater than 3.

20. 3. The method of claim 1 or 2, wherein the cyanoacrylate component further comprises an additive selected from the group consisting of impact additives, thixotropic agents, thickeners, dyes, thermal degradation enhancers, and combinations thereof.

21. 21. The method of claim 20, wherein the impact additive is citric acid.

22. 3. The method of claim 1 or 2, wherein the cyanoacrylate component further comprises at least one additive selected from the group consisting of 2-sulfobenzoic anhydride, triethylene glycol di(p-toluenesulfonate), trifluoroethyl p-toluenesulfonate, dimethyldioxolen-4-ylmethyl p-toluenesulfonate, p-toluenesulfonic anhydride, methanesulfonic anhydride, 1,3-propylene sulfite, dioxathiolane dioxide, 1,8-naphthosultone, 1,3-propane sultone, 1,4-butene sultone, allyl phenyl sulfone, 4-fluorophenyl sulfone, dibenzothiophene sulfone, bis(4-fluorophenyl) sulfone, ethyl p-toluenesulfonate, trifluoromethanesulfonic anhydride, ethylene sulfite, and combinations thereof.

23. 23. The method of claim 22, wherein the additive is selected from 1,8-naphthosultone and ethylene sulfite, and combinations thereof.

24. 1. A method for joining submerged substrates, comprising: applying a cyanoacrylate composition to at least one substrate in water, the cyanoacrylate composition comprising: (a) a first part, Contains a cyanoacrylate component and a rubber toughening agent, The rubber toughening agent comprises a first part comprising: (i) a reaction product of a combination of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site; (ii) a dipolymer of ethylene and methyl acrylate; or a combination of (i) and (ii); (b) a second part, 2-substituted benzothiazoles or derivatives thereof (wherein the 2-substituent is C １－２０ Alkyl group, C ２－２０ Alkene group, C ８－２０ Alkylbenzyl group, C １－２０ Alkylamino group, C １－２０ Alkoxy group, C １－２０ Alkylhydroxy group, ether group, sulfenamide group, C １－２０ Thioalkyl group or C １－２０ a second part comprising a thioalkoxy group; at least one of the first part or the second part further comprises an anhydride component; The second part is, a component containing at least two (meth)acrylate functional groups, present in an amount of 1 to 20 wt. %, preferably 4 to 12 wt. %, based on the total weight of the composition; and Hello, -NO ２ at least one benzonitrile compound substituted with at least two or more electron-withdrawing groups selected from —CN, —CN, or —CN and combinations thereof; and and curing the composition in water.

25. the 2-substituted benzothiazole of said cyanoacrylate composition is selected from the group consisting of 5-chloro-2-methylbenzothiazole, 2-methyl-1,3-benzothiazole, 2-(methylmercapto)-benzothiazole, 5-methoxy-2-methylbenzothiazole, 6-methoxybenzothiazole, 2,5-dimethylbenzothiazole, and 2-methyl-5-benzothiazolol, and combinations thereof; the anhydride component of the cyanoacrylate composition is selected from the group consisting of tetrafluoroisophthalonitrile, 3,5-dinitrobenzonitrile; 2-chloro-3,5-dinitrobenzonitrile; pentafluorobenzonitrile; α,α,α-2-tetrafluoro-p-tolunitrile; and tetrachloroterephthalonitrile, and combinations thereof; and 25. The method of claim 24, wherein the component of the cyanoacrylate composition containing at least two (meth)acrylate functional groups is selected from the group consisting of hexanediol diacrylate, hexanediol dimethacrylate, and di-trimethylolpropane tetraacrylate, and combinations thereof.

26. 3. The method of claim 1 or 2, wherein the cyanoacrylate composition is applied in a ratio of the first part to the second part of the cyanoacrylate composition ranging from about 1:1 to about 10:1, for example, 2:1, or 3:1, or 4:1, or 5:1, or 6:1, or 7:1, or 8:1, or 9:

1.

27. 25. The method of claim 24, wherein the cyanoacrylate composition is applied in a first part to second part ratio of about 10:

1.

28. 3. The method of claim 1, wherein the component of the cyanoacrylate composition containing at least two (meth)acrylate functional groups is used as a carrier material for at least one benzonitrile compound.

29. 3. The method of claim 1 or 2, comprising exposing the composition to water for up to 45 seconds prior to joining the surface of a second substrate with the coated surface of the first substrate.

30. The composition is cured to have a strength of at least 0.6 N / mm after 5 minutes of curing, e.g., after 24 hours of curing, e.g., after 168 hours. ２ 3. The method of claim 1 or 2, wherein a bond is formed having a shear strength of

31. The composition is cured to have a strength of at least 4 N / mm after 5 minutes of curing, e.g., after 24 hours of curing, e.g., after 168 hours. ２ 3. The method of claim 1 or 2, wherein a bond is formed having a shear strength of

32. 3. The method of claim 1 or 2, wherein one or both substrates are metallic, for example one or both substrates are steel.

33. 3. The method of claim 1 or 2, wherein one or both substrates comprise calcium carbonate, e.g., one or both substrates are shells, e.g., one or both substrates are shells of scleractinia.

34. 3. The method of claim 1 or 2, wherein the nozzle life is at least 4 minutes, such as at least 5 minutes.

35. 3. An assembly comprising two underwater substrates joined by the method of claim 1 or 2.

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