Underwater curable thermosetting composition

Abstract

Disclosed is a two-part system comprising a first component comprising one or more epoxy resins and an epoxy functional material having a functionality greater than 4 and a viscosity of less than 850 cps at 25 DEG C, and a second component comprising one or more phosphate esters having a functionality greater than 4 and a viscosity of less than 850 cps at 25 DEG C, wherein the first component is mixed with the second component at room temperature to form a composition having a peak overlap shear stress after curing under water of at least 7 MPa according to ASTM D1002-10.

Description

Technical Field

[0001] The present teachings generally relate to a room temperature activated thermosetting composition suitable for underwater curing, which comprises a first component and a second component, wherein the first component comprises at least one component containing epoxy functionality, and the second component comprises an acidic curing agent. Background Art

[0002] Metal and cementitious materials can degrade due to long-term exposure to wet or underwater environments. Underwater and wet conditions are considered to be very difficult working environments for these materials. After exposure to these conditions, these materials usually need to be maintained and / or strengthened. Current two-component underwater repair solutions have certain disadvantages. Generally, these existing two-part solutions are very viscous and difficult to mix and apply. Typically, they are provided as two separate parts rather than in a single cartridge. They also tend to be very slow-reacting systems that may take several hours to days to complete the reaction, or they require additional stimulation (such as ultraviolet (UV) light or heat) to quickly activate and cure. Another disadvantage of existing materials is that they are generally only recommended for limited substrate types and certain conditions, and are not recommended as more general repair options for underwater repair applications.

[0003] The present teaching solves one or more of the above problems by providing a two-component composition as a fast curing bonding solution. If necessary, they can be easily applied using a cartridge or other common two-component dispensing equipment. The compositions described herein are bonded to a variety of substrates, including but not limited to concrete, aluminum, stainless steel, wood and plastic.

[0004] The teachings herein facilitate simplifying the underwater remediation process by minimizing the steps and providing solutions applicable to a variety of substrates.

[0005] The present teachings relate to a fast-curing composition adapted to withstand underwater conditions, the fast-curing composition comprising at least one epoxy-functional ingredient on the A side and at least one acid on the B side. These two-component room temperature activated materials can cure in air. Typically, the presence of water may cause the curing agents to hydrolyze, thereby preventing them from curing (and possibly foaming). To minimize the effect of water on the curing characteristics of the composition, three main strategies have been used: repelling water with low energy materials; generating sufficient heat through exothermic reactions to evaporate or squeeze water away from the interface, even for a short time; and engaging with the interface between the substrate and the material composition and absorbing water from the interface.

[0006] This underwater repair solution provided herein has significant tensile and compressive strength, making it an ideal choice for difficult environments such as support columns, driveway drains, pool decks, etc. The underwater two-component material maintains the structural integrity of the substrate, stops leaks, and reduces the cost and time of repair. Another advantage of the two-component underwater solution is that no (or minimal) surface preparation is required prior to application.

[0007] The compositions described herein may or may not be foamed. If the material is foamed, the volume expansion of the foam may be 1% to 20%, although higher expansion percentages may be desired. Foaming may be preferred because it can help inject and fill small irregularities and cracks in cavities.

[0008] International PCT publications WO 2020 / 101732, WO 2020 / 205355, WO 2020 / 206346 and WO 2020 / 198139 describe the use of phosphoric acid and phosphate esters for curing compositions in situ. These compositions are commonly used in a variety of room temperature activated systems, such as rigid structural foams, cavity fillings, gaskets and sealants. The benefits of such compositions may include the ability to adhere to various substrates, contain low volatile organic compounds (VOCs), be insensitive to dispensing temperature, be insensitive to the precise mixing ratio of the two-part system, be able to adjust physical and mechanical properties, or any combination thereof. The focus of this teaching is a thermosetting composition that is suitable for curing under underwater conditions and can therefore repair many structures under damp, wet and / or underwater conditions. Summary of the invention

[0009] The present teachings provide a two-part system comprising: a first component comprising one or more epoxy resins; and an epoxy-functional material (compound) having an epoxy functionality greater than 4 and a viscosity less than 850 cps at 25° C. as measured according to ASTM D445. A second component comprising one or more phosphate esters is included. Upon mixing the first component with the second component at room temperature, a composition is formed, the composition having a peak lap shear stress after underwater curing of at least 7 MPa, and / or comprising or consisting essentially of 40 wt % to 85 wt % of one or more epoxy resins relative to the weight of the first component; preferably, wherein the one or more epoxy resins comprise or consist essentially of the following: a liquid epoxy resin, an epoxy phenol novolac resin, an epoxy resin dissolved in xylene, or a combination thereof; 0.5 wt % to 10 wt % of an epoxy functional material relative to the weight of the first component; preferably, wherein the epoxy functional material comprises or consists essentially of epoxidized linseed oil; 50 wt % to 90 wt % of one or more phosphate esters relative to the weight of the second component; and one or more additives in the first component and the second component.

[0010] The lap shear at peak stress after underwater curing according to the present invention is measured according to ASTM D1002-10 at 23°C.

[0011] For the purposes of this specification, the terms "two-part system" and "two-component system" are used interchangeably. The same applies in this context to the individual terms "part", "component" and "side", such as "A side" and "B side", unless otherwise expressly stated, the "first component" corresponds to the "first part" and "A side", respectively. Unless otherwise expressly stated, the "second component" corresponds to the "second part" and "B side", respectively.

[0012] After mixing the first component and the second component, the composition can be cured at a temperature of about 0° C. to about 50° C. The first component can include cement. The first component can include a silicone prepolymer.

[0013] The one or more phosphates may include phosphates derived from cashew nut shell liquid (CNSL). The one or more phosphates may include phosphates derived from 2-ethylhexyl glycidyl ether. The one or more phosphates may include phosphates derived from phenyl glycidyl ether. The one or more phosphates may include phosphates derived from epoxidized p-tert-butylphenol. The one or more phosphates may include nonylphenol ethoxylated phosphate.

[0014] The epoxy functional material can be epoxidized linseed oil. Said composition can include one or more additives, and these one or more additives are selected from core-shell polymers, metal carbonates, minerals, reinforcing fibers, hydrophobic silica, monomers, plate-like aluminum oxides or any combination thereof. Said composition can include metal carbonates, and this metal carbonate can be calcium carbonate existing in an amount of about 0.01 % by weight to about 10 % by weight. Said composition can include ultrafine calcium carbonate (about 1 micron average particle size), fine calcium carbonate (about 4 micron average particle sizes), medium fine calcium carbonate (about 22 micron average particle sizes) or any combination thereof.

[0015] One or both of the first component and the second component may include wollastonite. One or both of the first component and the second component may include fumed silica. The second component may include P2O5. The second component may include one or more of plate-like alumina, reinforcing fibers, hydrophobic silica, minerals, monomers, phosphoric acid, polyphosphoric acid, or any combination thereof.

[0016] The one or more epoxy resins and epoxy functional materials may include one or more liquid epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more phenoxy resins, one or more silane-modified epoxy resins, or any combination thereof. The composition may include one or more epoxy phenol novolac resins having a functionality of about 2 to about 3; epoxy phenol novolac resins having a functionality of about 3 to about 4; or both. The composition may include one or more epoxy phenol novolac resins present in an amount of about 20% by weight to about 50% by weight. The composition may include one or more silicone prepolymers present in an amount of at least 0.5% by weight.

[0017] The composition can be cured at a temperature of about 10° C. to about 50° C. The composition can be cured at a temperature of about 15° C. to about 25° C. The composition can be cured in water. The two-part system can be substantially free of a curing agent, a latent curing accelerator, or both (except for the phosphate ester).

[0018] The second component may include P2O5, polyphosphoric acid, or some combination thereof in an amount of about 1 wt % to about 15 wt %, preferably about 3 wt % to about 10 wt %, and even more preferably about 5 wt % to about 8 wt %, relative to the total weight of the second component.

[0019] The first component may include epoxy functional materials in an amount of about 0.1 wt % to about 15 wt %, preferably about 0.4 wt % to about 10 wt %, even more preferably about 1 wt % to about 7 wt % relative to the total weight of the first component.

[0020] The first component may include epoxidized linseed oil in an amount of about 0.1 wt % to about 15 wt %, preferably about 0.4 wt % to about 10 wt %, even more preferably about 1 wt % to about 7 wt %, relative to the total weight of the first component.

[0021] The first component may include Portland cement in an amount of about 0.1 wt % to about 10 wt %, preferably about 0.5 wt % to about 8 wt %, even more preferably about 0.9 wt % to about 5 wt %, relative to the total weight of the first component.

[0022] The first component may include an epoxy resin dissolved in xylene in an amount of about 0.5 wt % to about 30 wt %, preferably about 2 wt % to about 20 wt %, even more preferably about 5 wt % to about 15 wt %, relative to the total weight of the first component.

[0023] The resulting composition may include the first component and the second component in a ratio of about 5 parts by volume of the first component to about 1 part by volume of the second component. The resulting composition may include the first component and the second component in a ratio of about 4 parts by volume of the first component to about 1 part by volume of the second component. The resulting composition may include the first component and the second component in a ratio of about 3 parts by volume of the first component to about 1 part by volume of the second component.

[0024] The teachings herein further relate to a two-part system comprising: a liquid epoxy resin and an epoxy resin dissolved in xylene in a first component, an epoxy-functional material comprising epoxidized linseed oil in the first component, one or more phosphate esters in a second component, and P2O5, polyphosphoric acid, or some combination thereof in the second component. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Comparative test data for the formulations shown in Table 1 are shown.

[0026] Figure 2A and Figure 2B Comparative test data for the formulations shown in Table 1 are shown.

[0027] Figure 3 Comparative test data for the formulations shown in Table 1 are shown. DETAILED DESCRIPTION

[0028] This teaching satisfies one or more of the above-mentioned needs through the improved compositions and methods described herein. The explanations and descriptions presented herein are intended to familiarize those skilled in the art with this teaching, its principles and its practical applications. Those skilled in the art can modify and apply this teaching in its various forms, such as being able to make it most suitable for the needs of a particular purpose. Therefore, the specific embodiments of this teaching set forth are not intended to be exhaustive or limit this teaching. Therefore, the scope of this teaching should not be determined with reference to the above description, but should be determined with reference to the full scope of the equivalents given by the attached claims and such claims. The disclosures of all articles and references (including patent applications and publications) are incorporated by reference for all purposes. As will be understood from the following claims, other combinations are also possible, which are also incorporated by reference in this written specification.

[0029] This application claims the benefit of the filing date of U.S. Provisional Application No. 63 / 336,365, filed on April 29, 2022. The contents of that application are hereby incorporated by reference in their entirety for all purposes.

[0030] The present teachings relate to two-component underwater curing compositions that are capable of rapid bonding. They can be easily applied using cartridges or other common two-component dispensing equipment. They bond to a variety of substrates, including but not limited to concrete, aluminum, stainless steel, wood, and plastic. The nature of the material can shorten and simplify the underwater repair process by minimizing the steps and operations required by existing systems.

[0031] Typically, materials that are specified to be applied in air are not suitable for underwater dispensing. Therefore, it is desirable to create compositions that overcome this problem. It has been found that the compositions herein: (1) reduce the surface energy so as to produce a more hydrophobic material and repel water from the interface; (2) engage with water in such a way that it reacts with and absorbs water, thereby reducing the presence of water at the interface of the composition and the substrate; and (3) generate sufficient exotherm to evaporate some of the water at the interface in a short period of time.

[0032] Each of these strategies may have certain limitations when used alone. For example, if a formulation is made of many hydrophobic materials with low surface energy, the material may completely repel water, but wetting and subsequent bonding to many substrates may be difficult. On the other hand, if the material only absorbs and reacts with water, its long-term water resistance may be poor. Work to date suggests that combining two or more mechanisms may be beneficial to obtain an attractive balance of properties.

[0033] Underwater construction and repair is generally more difficult and more expensive than in dry conditions. Material choices are limited and there is a need for durable materials that can be applied easily and cure quickly.

[0034] Another advantage of the current invention is that no (or minimal) surface preparation is required prior to application. Most existing materials require careful surface preparation to ensure that the substrate is sufficiently clean prior to application; therefore, most technologies are not suitable for underwater repair applications, where surface preparation is difficult or perhaps impossible.

[0035] The composition of the present teachings can be a two-part composition ("two-part system"). The two-part system can include an A side ("first component") and a B side ("second component"). The A side and the B side can be mixed to form a mixed composition. The mixed composition can be cured to form a reaction product. The reaction product can be fully cured (i.e., without undergoing further crosslinking reactions). Curing can begin after mixing the A side and the B side. Curing can typically begin immediately after mixing the A side and the B side. Curing can be delayed for a period of time after mixing the A side and the B side. The two-part system can be free of latent curing agents, curing accelerators, or both.

[0036] The two-part system can be mixed at temperatures between about 0°C and 50°C. Curing of the two-part system can be initiated at room temperature. If desired, volume expansion can be increased by increasing the temperature of the mixed composition and / or increasing the temperature of the A-side and / or B-side while mixing. When dispensing, the ambient water temperature may not affect the foaming rate as much as the temperature of the two-part system.

[0037] Two-part systems can form thermoset materials.

[0038] The A side may include epoxidized linseed oil. Epoxidized linseed oil is a very low viscosity component with a high functionality (functionality of about 7) that promotes rapid curing. Epoxidized linseed oil is commonly used as a lubricant in paints and coatings. The combination of high functionality and low viscosity makes epoxidized linseed oil a very fast reacting and highly cross-linked material when cured using certain acidic curing agent compositions. The material is highly hydrophobic and tends to repel moisture and water from the substrate. The reaction of the epoxidized linseed oil on the A side with certain acidic substances on the B side may be highly exothermic. The epoxidized linseed oil component contributes to a mechanism for producing a suitable underwater repair solution. Due to its hydrophobicity and water evaporation caused by a highly exothermic reaction, the epoxidized linseed oil component helps to physically repel water. Several non-limiting examples of suitable epoxidized linseed oils may include Vikoflex 7190 from Cargill or Epoxol 9-5 from ACS Technical Products.

[0039] The A side may include one or more difunctional or multifunctional silicone prepolymers with epoxy terminal groups. A non-limiting example is Silmer EPC Di-50, which is a siloxane prepolymer with alicyclic epoxy groups. SilmerEPC Di-50 is a difunctional reactive polymer that can reduce the stiffness of the cured composition. This molecule is a very hydrophobic material that can react relatively quickly with the acidic material on the B side. The highly hydrophobic nature of the molecule helps repel water and moisture and improves bonding to the substrate.

[0040] Side A can include a type of water-curable cementitious material, such as cement. Cement is an inorganic material, usually based on calcium silicate. The presence of cement in the formulation can help absorb water (initial water and as water diffused into the bulk material). Almost immediate absorption can help to achieve the interaction of the organic part of the composition with the bonding interface. Compared with the rest of the formulated composition, cement solidification is slower. During solidification, cement is not water-soluble, therefore has good underwater durability. Portland cement is a non-limiting example of cement that can be used in the formulation.

[0041] Side A may include other materials that are capable of absorbing and / or reacting with water. Examples include garden plaster (calcium sulfate) and calcium oxide.

[0042] The A side may include one or more additional epoxy functional materials, which may include epoxy resins. The additional epoxy resins may include multifunctional aromatic epoxy resins, multifunctional aliphatic epoxy resins, silane-modified epoxy resins, epoxy / elastomer adducts, epoxidized natural products such as soybean oil, or any combination thereof.

[0043] The two-part system may include one or more polyfunctional aromatic and / or aliphatic epoxy resins. The polyfunctional aromatic and / or aliphatic epoxy resins may increase the crosslink density of the reaction product, improve the mechanical properties of the reaction product, improve the chemical resistance of the reaction product, increase the reaction rate, reduce the viscosity of the two-part system and / or the mixed composition, improve the cell structure quality of the reaction product after foaming, or any combination thereof. The functionality of the polyfunctional aromatic and / or aliphatic resin may be about 2.1 or greater, 3 or greater, or even 4 or greater. The functionality of the polyfunctional aromatic and / or aliphatic resin may be about 8 or less, 7 or less, or even 6 or less.

[0044] The two-part system can include one or more epoxy novolac resins. The epoxy novolac resin can be liquid or solid at room temperature. The two-part system can include one or more liquid epoxy novolac resins, one or more solid epoxy novolac resins or both. The epoxy novolac resin can have a functionality of about 2.1 to 6.5. The epoxy novolac resin can play a role in improving the crosslinking density of the reaction product, increasing the reaction rate, improving the glass transition temperature, improving mechanical properties, improving chemical resistance, improving moisture resistance or any combination thereof. The epoxy novolac resin is a hydrophobic molecule, and when reacting with an acid group, the epoxy novolac resin reacts very fast and is exothermic.

[0045] Side A can include one or more epoxy-based materials (i.e., one or more epoxy resins). The one or more epoxy resins can be any conventional dimerization, oligomerization or polymerization epoxy resin. The one or more epoxy resins can contain at least one epoxy functional group (i.e., monofunctional) or can contain more than one epoxy functional group (i.e., multifunctional). The one or more epoxy resins can contain one or more epoxy functional groups, two or more epoxy functional groups, three or more epoxy functional groups or even four or more epoxy functional groups. The one or more epoxy resins can be modified epoxy resins (e.g., silane-modified, elastomer-modified, etc.). The one or more epoxy resins can be aliphatic, alicyclic, aromatic, etc. or any combination thereof. The one or more epoxy resins can be supplied as solid (e.g., as pellets, blocks, sheets, etc. or any combination thereof) or liquid (e.g., liquid epoxy resin). As used herein, unless otherwise specified, an epoxy resin is solid if it is solid at a temperature of 23°C, and is a liquid resin if it is liquid at a temperature of 23°C. The one or more epoxy resins may include one or more liquid epoxy resins, one or more flexible epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more reactive diluents, one or more phenoxy resins, one or more silane-modified epoxy resins, or any combination thereof.

[0046] The two-part system may include one or more liquid epoxy resins. The liquid epoxy resin may serve as a base for the epoxy resin component. The liquid epoxy resin may be a reaction product of epichlorohydrin (hereinafter referred to as "EPH") and any conventional bisphenol. The liquid epoxy resin may be a reaction product of EPH and bisphenol A (hereinafter referred to as "BPA"), bisphenol F (hereinafter referred to as "BPF"), or both. The liquid epoxy resin may have an epoxy equivalent weight (hereinafter referred to as "EEW") of about 160 g / equivalent to about 192 g / equivalent as measured according to ASTM D1652-97. The liquid epoxy resin may have an epoxy percentage of about 20 to about 25. The liquid epoxy resin may have a viscosity of about 2,000 cP to about 14,000 cP at 25°C as measured according to ASTM D445. An example of a suitable BPA-based liquid epoxy resin may be DER TM 331, commercially available from The Olin Corporation, Clayton, MO. An example of a suitable BPF-based liquid epoxy resin may be YDF-170, commercially available from Kukdo Chemical (Korea).

[0047] The liquid epoxy resin may be present as part of the A side. The liquid epoxy resin may be present in an amount of about 4% to about 70% by weight of the A side. The liquid epoxy resin may be present in an amount of about 6% to about 10% by weight of the A side. The liquid epoxy resin may be present in an amount of about 8% by weight of the A side.

[0048] The two-part system may include one or more flexible epoxy resins. The one or more flexible epoxy resins may serve to reduce the compression modulus of the reaction product, increase the failure strain, reduce the recovery time, reduce the degree of crosslink density, increase impact resistance, improve adhesion, improve peel resistance, or any combination thereof. To the extent that the resulting composition is foamed, the one or more flexible epoxy resins may improve the gas entrapment capacity of the two-part system by acting as a viscosity modifier. The one or more flexible epoxy resins may be a difunctional glycidyl ether epoxy resin, an unmodified BPA-based epoxy resin, a multifunctional epoxidized polybutadiene resin, or any combination thereof. The one or more flexible epoxy resins may have an EEW of about 260 to about 500 as measured according to ASTM D1652-97. The one or more flexible epoxy resins may have a viscosity of about 700 cP to about 25,000 cP at 25°C as measured according to ASTM D445. Examples of suitable flexible epoxy resins may include NC-514 (commercially available from Cardolite Corporation of Monmouth Junction, New Jersey), PY4122 (commercially available from Huntsman Advanced Materials, Inc., Salt Lake City, UT), Poly 605E (commercially available from Cray Valley, Exton, PA), or any combination thereof.

[0049] The one or more flexible epoxy resins may be present on the A side. The one or more flexible epoxy resins may be present in an amount of about 0.5 wt % to about 40 wt % of the A side. The one or more flexible epoxy resins may be present in an amount of about 35 wt % to about 45 wt % of the A side. The one or more flexible epoxy resins may be present in an amount of about 39 wt % of the A side. The one or more flexible epoxy resins may include a difunctional glycidyl ether epoxy resin in an amount of about 10 wt % to about 18 wt % of the A side, an unmodified BPA-based epoxy resin in an amount of about 8 wt % to about 16 wt % of the A side, and a multifunctional epoxidized polybutadiene resin in an amount of about 8 wt % to about 16 wt % of the A side. The one or more flexible epoxy resins may include a difunctional glycidyl ether epoxy resin in an amount of about 5% to 20% by weight of the A side, an unmodified BPA-based epoxy resin in an amount of about 5% to about 20% by weight of the A side, and a multifunctional epoxidized polybutadiene resin in an amount of about 5% to about 20% by weight of the A side. The two-component system may include a difunctional glycidyl ether epoxy resin, a difunctional epoxy resin derived from cardanol, and a multifunctional epoxidized polybutadiene resin, respectively, in a ratio of about 1:1:1. The two-component system may include a difunctional glycidyl ether epoxy resin, a difunctional epoxy resin derived from cardanol, and a multifunctional epoxidized polybutadiene resin. The above resins may be present in a ratio of about 1:0.8:0.8, respectively. The two-component system may include a difunctional glycidyl ether epoxy resin, a difunctional epoxy resin derived from cardanol, and a multifunctional epoxidized polybutadiene resin. The above resins may be present in a ratio of about 1:0.9:0.9, respectively.

[0050] The two-part system described herein may also include one or more epoxy phenol novolac resins. The one or more epoxy phenol novolac resins may serve to impart chemical resistance, solvent resistance, temperature resistance, or any combination thereof to the reaction product. The one or more epoxy phenol novolac resins may be present as part of the A side. The one or more epoxy phenol novolac resins may have an EEW of about 165 g / equivalent to about 183 g / equivalent as measured according to ASTM D1652-97. The one or more epoxy phenol novolac resins may have an average epoxy functionality of about 2.1 to about 6.5. The one or more epoxy phenol novolac resins may have a viscosity of about 18,000 cP to about 30,000 cP at 25 ° C as measured according to ASTM D445. Examples of suitable epoxy phenol novolac resins may be those sold under the following trade names: 8250 (oligomeric reaction products of formaldehyde with 1-chloro-2,3-propylene oxide and phenol; functionality 2.6) and 8330 (poly[(phenyl glycidyl ether)-co-formaldehyde]; 3.6 functionality), commercially available from Huntsman Corporation.

[0051] The one or more epoxy phenol novolac resins may be present in an amount of about 10% by weight to about 60% by weight of the A side. The one or more epoxy phenol novolac resins may be present in an amount of about 35% by weight to about 45% by weight of the first component or the A side. The one or more epoxy phenol novolac resins may be present in an amount of about 38% by weight to about 42% by weight of the A side. The one or more epoxy phenol novolac resins may be present in an amount of about 42% by weight of the A side. The one or more epoxy phenol novolac resins may include about 3.6 functional epoxy phenol novolac resins present in an amount of about 0.1% by weight to about 50% by weight of the A side and about 6.5 functional epoxy novolac resins present in an amount of about 22% by weight to about 32% by weight of the A side. The one or more epoxy phenol novolac resins may include an about 3.6 functional epoxy phenol novolac resin present in an amount of about 15 wt % of the A side and an about 6.5 functional epoxy novolac resin present in an amount of about 28 wt % of the A side. The two part system may include an about 3.6 functional epoxy phenol novolac resin to an about 6.5 functional epoxy phenol novolac resin in a ratio of about 1:2 to about 1:3.

[0052] The two-part system may include one or more aliphatic multifunctional epoxy resins. The one or more aliphatic multifunctional epoxy resins may serve to increase the degree of crosslinking of the reaction product, increase the chemical resistance of the reaction product, or both. The one or more aliphatic multifunctional epoxy resins may include epoxidized sorbitol. The one or more aliphatic multifunctional epoxy resins may have an EEW of about 160 g / equivalent to about 195 g / equivalent as measured according to ASTM D1652-97. The one or more aliphatic multifunctional epoxy resins may have a viscosity of about 4,000 cP to about 18,000 cP at 25° C. as measured according to ASTM D445. Examples of suitable aliphatic multifunctional epoxy resins may be those sold under the trade name GE-60 and Those sold as GE-61 are commercially available from Huntsman Corporation.

[0053] The one or more aliphatic multifunctional epoxy resins may be present as part of the A side. The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 4 wt % to about 60 wt % of the A side. The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 10 wt % to about 22 wt % of the A side. The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 20 wt % of the A side. The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 13 wt % of the A side.

[0054] The two-part system may include one or more reactive diluents. For multifunctional diluents, the one or more reactive diluents may act to reduce the overall viscosity of the two-part system so as to modify the dispensing process or the flow of the two-part system on the workpiece after dispensing, increase the degree of crosslinking of the reaction product, or both. The one or more reactive diluents may be polymeric, whereby the reactive diluent may increase the flexibility of the reaction product; the one or more reactive diluents may be multifunctional, whereby the reactive diluent may promote increased crosslinking and impart chemical resistance to the reaction product; or both. The one or more reactive diluents may include polyethylene glycol diglycidyl ether, trimethylolethane triglycidyl, or both. The one or more reactive diluents may have an EEW of about 150 g / equivalent to about 170 g / equivalent as measured according to ASTM D 1652-97. The one or more reactive diluents may have a viscosity of about 200 cP to about 300 cP at 25°C as measured according to ASTM D445. Examples of suitable reactive diluents may be those sold under the trade name GE-31 and Those sold as GE-24 are commercially available from Huntsman Corporation.

[0055] The one or more reactive diluents may be present in an amount of about 5% to about 20% by weight of the A side. The one or more reactive diluents may be present in an amount of about 8% to about 16% by weight of the A side. The one or more reactive diluents may be present in an amount of about 10% to about 14% by weight of the A side. The one or more reactive diluents may be present in an amount of about 13% by weight of the A side. The one or more reactive diluents may include polyethylene glycol diglycidyl ether present in an amount of about 2% to about 6% by weight of the A side, and trimethylolethane triglycidyl ether present in an amount of about 6% to about 14% by weight of the A side. The one or more reactive diluents may include polyethylene glycol diglycidyl ether present in an amount of about 4% by weight of the A side, and trimethylolethane triglycidyl ether present in an amount of about 9% by weight of the A side. The two-part system may include polyethylene glycol diglycidyl ether and trimethylolethane triglycidyl ether in a ratio of about 1:2 to about 1:3, respectively.

[0056] The two-part system can include one or more phenoxy resins (i.e., polyhydroxy ethers). The one or more phenoxy resins can serve to impart improved adhesion, corrosion resistance, heat resistance, or any combination thereof to the reaction product. The one or more phenoxy resins can be derived from the reaction of BPA and EPH. The one or more phenoxy resins can have terminal hydroxyl groups and hydroxyl groups in each repeating polymer unit. When dissolved in a solvent, the one or more phenoxy resins can have an EEW of about 202 g / equivalent to about 214 g / equivalent as measured according to ASTM D 1652-97. The one or more phenoxy resins can have a viscosity of about 20,000 cP to about 50,000 cP at 25 ° C as measured according to ASTM D445. An example of a suitable phenoxy resin can be Phenoxy LER-HB commercially available from Huntsman.

[0057] The one or more phenoxy resins may be present in an amount of about 1 wt % to about 20 wt % of the A side. The one or more phenoxy resins may be present in an amount of about 7 wt % to about 12 wt % of the A side. The one or more phenoxy resins may be present in an amount of about 10 wt % of the A side.

[0058] The two-part system can include one or more tougheners. The one or more tougheners can play the role of distributing energy in the reaction product (that is, increasing impact resistance). The one or more tougheners can facilitate the T peel strength of increase. The one or more tougheners can include thermoplastics, thermosetting plastics or thermosetting plastics, elastomers, etc. or any combination thereof. The one or more tougheners can include elastomers (including elastomer-containing materials), core-shell polymers (which can include but are not limited to elastomers) or both.

[0059] Core-shell polymers (if present) can include a first polymer material (i.e., core material) and a second polymer material (i.e., shell material). The first polymer material can be completely encapsulated by the second polymer material. Core-shell polymers can include an amount of about 30% by weight or more, 50% by weight or more, or even 70% by weight or more of the first polymer material. The first polymer material, the second polymer material, or both can include one, two, three, or even more than three polymers combined together, reacted together (e.g., sequentially polymerized) or both, or can be a part of a separate or identical core-shell polymer system. Examples of suitable core-shell polymers can be those sold under the trade name Kane MX-267 and MX-257 are core-shell polymers sold commercially from Kaneka North America LLC in Pasadena, TX.

[0060] Core-shell polymers can be present in an amount of about 1% by weight to about 25% by weight of a combination of side A, side B, or side A and side B (e.g., if present in an amount of 10% by weight, it can be present in an amount of 5% by weight to 5% by weight of side A and side B). Core-shell polymers can be present in an amount of about 5% by weight to about 20% by weight of a combination of side A, side B, or side A and side B. Core-shell polymers can be present in an amount of about 5% by weight to about 5% by weight of a combination of side A, side B, or side A and side B. Core-shell polymers can be present in an amount of about 17% by weight of a combination of side A, side B, or side A and side B.

[0061] The two-part system can include one or more core-shell particle polymers. The core-shell particle polymer can serve to improve the fracture toughness, impact resistance, peel resistance and ductility of the reaction product. Epoxy resin formulations are generally used for applications requiring rigidity and high temperature resistance. Unmodified standard epoxy resins are often brittle. There are different strategies to reduce the brittleness of epoxy resins. Typically, toughening agents such as core-shell polymer microparticles are used to reduce the brittleness of the reaction product and improve its ductility without significantly affecting temperature resistance because they are discrete microparticles that are not a part of the continuous phase.

[0062] The core-shell particle polymer may be present in the A side, the B side, or both. The core-shell particle polymer may be present in an amount of about 5 wt % or more, 10 wt % or more, or even 15 wt % or more of the A side or the B side. The core-shell particle polymer may be present in an amount of about 35 wt % or less, 30 wt % or less, or even 25 wt % or less of the A side or the B side.

[0063] The core-shell particle polymer can be pre-dispersed in the epoxy resin. The core-shell particle polymer can be dispersed in the epoxy resin based on bisphenol A. The epoxy resin mixture can be a liquid epoxy resin. The epoxy resin can have a viscosity of about 16,000cP to about 20,000cP, more preferably 17,000cP to 19,000cP or even more preferably about 18,000cP measured at 50°C according to ASTMD445-21. The core-shell particle polymer can be present in the epoxy resin in an amount of about 30% to 45%, more preferably 35% to 40% or even more preferably about 37%. The core-shell particle polymer can have a median particle size of about 100nm to 300nm or even about 200nm. The core-shell particle polymer can include polybutadiene. Non-limiting examples of suitable core-shell particle polymers can include Kane Ace MX-257 and MX-267, which are specific products in which the core-shell has been distributed in the epoxy resin, commercially available from Kaneka Corporation. Alternatively, powdered core / shell materials such as E-950 commercially available from Arkema Corporation can also be used in the composition.

[0064] The two-part system can include one or more silane-modified epoxy resins. The silane-modified epoxy resin can play a role in imparting improved adhesion to the reaction product. Adhesion can be adhesion to glass, metal or both. The silane group can form a covalent bond with the epoxy resin and the inorganic substrate. The silane-modified epoxy resin can be present on the A side. The silane-modified epoxy resin can be present in an amount of about 0.5% by weight or more, 1% by weight or more, 2% by weight or more, or even 3% by weight or more of the A side. The silane-modified epoxy resin can be present in an amount of about 10% by weight or less, 9% by weight or less, 8% by weight or less, or even 7% by weight or less of the A side. The one or more silane-modified epoxy resins can be present in an amount of about 1% by weight to about 7% by weight of the A side. The one or more silane-modified epoxy resins can be present in an amount of about 2% by weight to about 6% by weight of the A side. The one or more silane-modified epoxy resins can be present in an amount of about 4% by weight of the A side.

[0065] The silane-modified epoxy resin can have an epoxy equivalent weight of about 170 g / eq to 240 g / eq according to ASTM D 1652-11, more preferably about 180 g / eq to 230 g / eq, or even more preferably about 190 g / eq to 220 g / eq. The silane-modified epoxy resin can have a viscosity of about 7,000 cP to 17,000 cP, more preferably about 8,000 cP to 16,000 cP, or even more preferably about 9,000 cP to 15,000 cP measured at 25 ° C. Non-limiting examples of suitable silane-modified epoxy resins can include Epokukdo KSR 177, which is commercially available from Kukdu Chemical Co., Ltd.

[0066] The silane-modified epoxy resin can be a linear bifunctional silicone prepolymer (e.g., a prepolymer having alicyclic epoxy groups) terminated with a cyclic epoxide. Another suitable material is a silicone prepolymer having alicyclic epoxy groups. An example of such a material can be obtained from Siltech Corporation of Ontario, Canada under the trade name SilmerEPC Di-50.

[0067] The two-part system may include a metal carbonate material. The metal carbonate material may be calcium carbonate. The calcium carbonate may have a median particle size of about 1 micron to about 50 microns. The calcium carbonate may be medium sized. For example, the median particle size of medium calcium carbonate may be about 22 microns. Examples of suitable medium fine calcium carbonate may be Q200, commercially available from Huber Engineered Materials of Atlanta, GA. The calcium carbonate may be finely sized. For example, the median particle size of the fine calcium carbonate may be about 4 microns. An example of a suitable fine calcium carbonate may be Q4, commercially available from Huber Engineered Materials in Atlanta, Georgia. The calcium carbonate can be ultrafine sized. For example, the median particle size of the ultrafine calcium carbonate can be about 1 micron. An example of a suitable ultrafine calcium carbonate can be Q 1, commercially available from Huber Engineered Materials, Atlanta, Ga. The two-part system may include medium fine calcium carbonate, fine calcium carbonate, ultrafine calcium carbonate, or any combination thereof.

[0068] When a two-part system includes a metal carbonate in the A side, the average functionality of the B side may be partially reduced when combined with the A side in the mixed composition. This may be due to the acid on the B side reacting with the metal carbonate on the A side to cause foaming. The A side may include components with increased functionality to compensate for the reduced functionality of the B side. The A side can be formulated with increased functionality by using reactive ingredients with a functionality greater than 2, such as aliphatic multifunctional epoxy resins.

[0069] The B side may include one or more acids. The acid may be liquid at room temperature. As described herein, room temperature may mean a temperature of about 20°C to 25°C. The acid may include a phosphate ester, phosphoric acid, citric acid, acetic acid, or any acid that is stable when mixed with phosphoric acid or a phosphate ester. The acid may include at least a phosphate ester, and optionally phosphoric acid, liquid polyphosphoric acid, citric acid, acetic acid, or any combination thereof.

[0070] The working time of the mixed composition can be adjusted by the choice of acid. Using a phosphate ester instead of phosphoric acid can delay the curing reaction due to its higher pH, lower functionality, higher viscosity, or any combination thereof. The functionality and pH of the phosphate ester can be selected to adjust the working time.

[0071] The B side can include phosphorus pentoxide (PO) as the anhydride of phosphoric acid. This white crystalline solid can react with water or moisture, generating excess heat, and convert to phosphoric acid. The reaction is very rapid and highly exothermic. The phosphoric acid can then react with the epoxy groups or metal carbonates from the A side. This material contributes to the two mechanisms we are interested in. Absorbing and reacting with water, and also generating heat to evaporate the water from the substrate.

[0072] The B side may include one or more phosphates, phosphate precursors, or both. The one or more phosphates may be pre-reacted. The B side may include one or more phosphate precursors, which may be combined with phosphoric acid prior to combining with the A side.

[0073] The B side may include additional phosphoric acid. The additional phosphoric acid may include orthophosphoric acid, polyphosphoric acid, or both. The additional phosphoric acid may increase the crosslink density and shorten the reaction time. The reaction rate of the pre-reacted phosphate ester may be increased by adding additional phosphoric acid to the B side. The additional phosphoric acid may increase the foaming of the mixed composition.

[0074] Side A can include one or more epoxy resins, one or more additives, one or more monomers or any combination thereof. The one or more epoxy resins can include one or more liquid epoxy resins, one or more flexible epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more reactive diluents, one or more phenoxy resins, one or more silane-modified epoxy resins, one or more monomers or any combination thereof. The one or more additives can include one or more toughening agents (e.g., core-shell polymers), metal carbonates, minerals, reinforcing fibers or other reinforcing particles, hydrophobic silica, plate-like alumina or any combination thereof.

[0075] The B side may include one or more phosphates, phosphoric acid, one or more additives, one or more monomers or any combination thereof. The one or more phosphates may include the first phosphate, the second phosphate, the third phosphate or any combination thereof. The one or more additives may include one or more toughening agents (e.g., core-shell polymers), minerals, reinforcing fibers or other reinforcing particles, hydrophobic silica, plate-like alumina or any combination thereof.

[0076] The one or more phosphates can be one or more customized phosphates. The one or more customized phosphates can be produced by the reaction of phosphoric acid and various alcohols. The one or more customized phosphates can be produced by the reaction of phosphoric acid with an epoxy group of a phosphate precursor (i.e., a component that has not yet reacted with phosphoric acid). The one or more customized phosphates can be produced by the reaction of phosphoric acid with a glycidyl ether of cashew nut shell liquid (CNSL) (such as those sold under the trade name LITE 2513HP, commercially available from Cardolite Corporation, Monmouth Junction NJ). The one or more customized phosphate esters can be produced by reacting phosphoric acid with phenyl glycidyl ether (such as sold under the trade name The one or more customized phosphate esters can be produced by reacting phosphoric acid with 2-ethylhexyl glycidyl ether (such as phenyl glycidyl ether sold under the trade name GE-13, commercially available from Huntsman Corporation). The one or more customized phosphate esters can be produced by reacting phosphoric acid with epoxidized p-tert-butylphenol (such as 2-ethylhexyl glycidyl ether sold under the trade name GE-6, commercially available from Huntsman Corporation). It is produced by the reaction of epoxidized p-tert-butylphenol sold as GE-11, commercially available from Huntsman Corporation).

[0077] The one or more phosphate esters may be one or more commercially available phosphate esters. When one or more commercially available phosphate esters are exchanged into the B side in place of a customized phosphate ester, they may produce a curable composition that reacts more slowly and foams, probably due to a lower amount of free phosphoric acid. The reaction and foaming of the one or more commercially available phosphate esters can be improved (i.e., accelerated) by adding phosphoric acid to the B side. The pH of the one or more commercially available phosphate esters in aqueous solution may be about 1 to 3. The one or more commercially available phosphate esters may have a viscosity of about 32,500 cP to about 42,500 cP at 25 ° C as measured according to ASTM D445. The one or more commercially available phosphate esters may be nonylphenol ethoxylated phosphate esters. An example of a suitable commercially available phosphate ester may be commercially available from Ashland, Inc. of Covington, KY, under the trade name Dextrol TM Those sold as OC-110, Dextrol OC-40, and Strodex MO-100.

[0078] Commercially available phosphates may be present on the B side. The one or more commercially available phosphates may be present in an amount of about 6 wt % to about 18 wt % of the B side. The one or more commercially available phosphates may be present in an amount of about 8 wt % to about 16 wt % of the B side. The one or more commercially available phosphates may be present in an amount of about 10 wt % to about 14 wt % of the B side. The one or more commercially available phosphates may be present in an amount of about 12 wt % of the B side.

[0079] The one or more phosphate esters can be produced by reacting a phosphate ester precursor with phosphoric acid in a series of stoichiometric ratios. The one or more phosphate esters can be produced by reacting a phosphate ester precursor with phosphoric acid at a ratio of about 0.7:1 to about 1:0.7. The one or more phosphate esters can be produced by reacting a phosphate ester precursor with phosphoric acid at a ratio of about 0.8:1 to about 1:0.8. The one or more phosphate esters can be produced by reacting a phosphate ester precursor with phosphoric acid at a ratio of about 0.9:1 to about 1:0.9. The one or more phosphate esters can be produced by reacting a phosphate ester precursor with phosphoric acid at a ratio of about 1:1. The one or more phosphate esters can be produced by reacting a phosphate ester precursor with phosphoric acid at a ratio of about 0.8:1.

[0080] The one or more phosphate esters may be selected from monoesters, diesters or triesters as shown below:

[0081]

[0082] The one or more phosphate esters can be obtained from the reaction of epoxy groups with phosphoric acid as shown below:

[0083]

[0084] The B side may include one or more phosphate esters, one or more phosphate ester precursors, or both. The B side may include one or more phosphate ester precursors, which may be combined with phosphoric acid prior to being combined with the A side. The B side may include one or more phosphate esters, which are pre-reacted (i.e., the epoxide and phosphate ester react) prior to being added to the B side.

[0085] The first phosphate ester can be the reaction product of phosphoric acid and 2-ethylhexyl glycidyl ether. The second phosphate ester can be the reaction product of epoxidized p-tert-butylphenol, the reaction product of the glycidyl ether of cashew nut shell liquid (CNSL), nonylphenol ethoxylated phosphate ester or a combination thereof. The third phosphate ester can be the reaction product of phosphoric acid and phenyl glycidyl ether. Side B can include the first phosphate ester, the second phosphate ester, the third phosphate ester or a combination thereof.

[0086] The first phosphate ester may be present in an amount of about 1% to about 70% by weight of the B side. The first phosphate ester may be present in an amount of about 5% to about 60% by weight of the B side. The first phosphate ester may be present in an amount of about 10% to about 30% by weight of the B side. The second phosphate ester, if present, may be present in an amount of about 1% to about 80% by weight of the B side. The second phosphate ester may be present in an amount of about 3% to about 50% by weight of the B side. The second phosphate ester may be present in an amount of about 5% to about 40% by weight of the B side. The third phosphate ester, if present, may be present in an amount of about 0.5% to about 90% by weight of the B side. The third phosphate ester may be present in an amount of about 10% to about 70% by weight of the B side. The third phosphate ester may be present in an amount of about 20% to about 65% by weight of the B side.

[0087] The B side may include phosphoric acid. The phosphoric acid may be orthophosphoric acid, polyphosphoric acid, or both. The phosphoric acid may be polyphosphoric acid. The phosphoric acid may be a free acid in one or more phosphate esters, phosphoric acid added independently of one or more phosphate esters, or both. Adding phosphoric acid to the B side may result in increased expansion (e.g., foaming) of the resulting reaction product. When the temperature is below 23° C., adding phosphoric acid to the B side may increase the reactivity of the two-part system to help maintain the desired expansion level, cure level, or both.

[0088] Independently added phosphoric acid, if present, may be in an aqueous solution (i.e., "reagent grade") in an amount of 85% or more or even 95% or more. Independently added phosphoric acid may be present in an amount of about 0.1% to about 30% by weight of the B side. Independently added phosphoric acid may be present in an amount of about 2% to about 6% by weight of the B side. Independently added phosphoric acid may be present in an amount of about 4% by weight of the B side.

[0089] The one or more phosphates produced by the reaction of phosphoric acid with one or more epoxy group-containing components may include free acid. The one or more phosphates may have about 1% or more free acid, about 3% or more free acid, about 5% or more free acid, about 15% or less free acid, about 13% or less free acid, or even about 11% or less free acid.

[0090] The one or more phosphates produced by reacting anhydrous phosphorus-containing moieties (such as phosphoric anhydride, phosphorus oxychloride or polyphosphoric acid) with one or more components containing alcohol groups may include free acids. The one or more phosphates may have about 1% or more free acids, about 3% or more free acids, about 5% or more free acids, about 15% or less free acids, about 13% or less free acids, or even about 11% or less free acids.

[0091] After the A-side and B-side are added, the two-component system may be used as a chemical blowing agent by foaming due to the reaction of the metal carbonate or metal bicarbonate with the acid, which produces the release of a gas (e.g., carbon dioxide). This reaction mechanism is described in U.S. Pat. No. 5,648,401, which is incorporated herein by reference for all purposes.

[0092] Curing, foaming or both can occur at a temperature of about 50°C or less, 40°C or less, about 30°C or less, about 20°C or less, or about 0°C or less. Curing, foaming or both can occur at a temperature of about 0°C or more, about 10°C or more, or even about 20°C or more. Curing, foaming or both can occur at a temperature of about 10°C to about 50°C or even more. Curing, foaming or both can occur at a temperature of about 10°C. Curing, foaming or both can occur at room temperature (e.g., at a temperature of about 15°C to about 25°C). Curing, foaming or both can occur at a temperature of about 23°C. Curing and foaming can occur at different temperatures or at substantially the same temperature. As previously described, the system described herein may not contain any foaming. The system described herein may include only minimal foaming (e.g., 0.5% to about 2% volume expansion).

[0093] Compared with other curing agents or curing systems that occur when not adding stimulation (for example, at room temperature), this teaching envisions relatively fast curing time, foaming time or both.The curing time of reaction product can be 75 minutes or shorter, 50 minutes or shorter, 30 minutes or shorter, 20 minutes or shorter, 2 minutes or longer, 8 minutes or longer or even 16 minutes or longer.The curing time of gained reaction product can be about 5 minutes to about 20 minutes.The curing time of gained reaction product can be about 10 minutes.The curing time of gained reaction product can be about 7 minutes.The curing time of gained reaction product can be about 5 minutes.Solidification and foaming can occur at different times or substantially simultaneously.

[0094] Foaming (if any) can start before the resulting reaction product is fully cured. The foaming time of the reaction product (i.e., the time range in which the two-part system actively foams) can be 30 minutes or less or even 20 minutes or less. The foaming time of the reaction product can be from about 1 minute to about 10 minutes. The foaming time of the reaction product can be about 5 minutes. The foaming time of the reaction product can be about 7 minutes.

[0095] The cure rate, degree of crosslinking, or both may be a function of the functionality of the two-part system (A side and B side). For two-part systems with prepolymer components of shorter polymer length (i.e., lower viscosity), higher functionality (i.e., the number of functional groups on one or more polymerizable components) may be desirable; thus, the lack of structural backbone caused by the shorter polymer is compensated by a higher degree of crosslinking. For two-part systems with prepolymer components of longer length (i.e., higher viscosity), lower functionality may be desirable; thus, the presence of more structural backbone caused by the longer polymer eliminates the need for high functionality.

[0096] The B-side functionality can be reduced at least in part by reaction of the metal carbonate in the A-side with phosphoric acid and phosphate esters. Thus, the functionality of the B-side in the in situ reaction mixture can be reduced. The A-side can include components with increased functionality to compensate for the reduced functionality of the B-side. The A-side can be formulated to have increased functionality by using reactive ingredients with a functionality greater than 2.

[0097] The two-part system may include one or more additives. The one or more additives may include one or more toughening agents, metal carbonates, reinforcing fibers or other reinforcing particles, hydrophobic silica, platy alumina, or any combination thereof.

[0098] The two-part system can include one or more minerals. The one or more minerals (i.e., "mineral reinforcement") can play a role in structurally strengthening the reaction product. The one or more minerals can improve the tensile strength, flexural strength or both of the reaction product. The one or more minerals can be any suitable silicate minerals, including but not limited to chain silicates (e.g., wollastonite) and phyllosilicates (e.g., kaolinite, vermiculite, talc, muscovite, etc.). The characteristic external shape of a single crystal or a crystal group of the one or more minerals can be needle-like or needle-like. The median particle size of the one or more minerals can be about 10 microns to about 20 microns. The median particle size can be about 12 microns to about 18 microns.

[0099] The one or more minerals may include wollastonite (CaSiO3). The wollastonite may be relatively pure (i.e., less than 2% by weight of impurities, such as other metal oxides). The wollastonite may contain impurities, including one or more oxides of iron, magnesium, manganese, aluminum, potassium, sodium, or strontium, replacing calcium in the mineral structure. An example of a suitable wollastonite may be obtained under the trade name 12 and 8 Wollastonite is commercially available from NYCO Minerals Inc. of Willsboro, NY.

[0100] The one or more minerals may be present as part of the A side, the B side, or both. Wollastonite may be present in an amount of about 1 wt % to about 18 wt % of the A side, the B side, or a combination of the A side and the B side. Wollastonite may be present in an amount of about 3 wt % to about 7 wt % of the A side, the B side, or a combination of the A side and the B side. Wollastonite may be present in an amount of about 4 wt % of the A side, the B side, or a combination of the A side and the B side.

[0101] The two-part system may include one or more reinforcing fibers. The reinforcing fibers may serve to structurally reinforce the reaction product. The one or more reinforcing fibers may improve the tensile strength, flexural strength, or both of the reaction product. The one or more reinforcing fibers may be present in the A side, the B side, or both. The one or more reinforcing fibers may be uniformly dispersed in the A side, the B side, or both. The one or more reinforcing fibers may comprise polymer fibers, glass fibers (i.e., fiberglass), or both. Polymer fibers may include nylon, polyamide, polyester, polypropylene, polyethylene, polytetrafluoroethylene, aramid fibers (e.g., ) or any combination thereof. The glass fibers may include aluminoborosilicate glass ("E-glass"), alkali-lime glass ("A-glass" or "C-glass"), electrically / chemically resistant glass ("E-CR-glass"), borosilicate glass ("D-glass"), aluminosilicate glass ("R-glass" or "S-glass"), or any combination thereof. The reinforcing fibers may be chopped fibers. The reinforcing fibers may be chopped lengths of about 0.1 cm or greater, about 0.3 cm or greater, or even about 0.6 cm or greater. The reinforcing fibers may be chopped lengths of about 2.0 cm or less, about 1.5 cm or less, or even about 1.0 cm or less. An example of a suitable glass fiber may be chopped strands commercially available from Jushi USA in Columbia, SC.

[0102] The reinforcing fibers may be present in an amount of about 0.01 wt % to about 15 wt % of the A side, the B side, or a combination of the A side and the B side. The reinforcing fibers may be present in an amount of about 1 wt % to about 10 wt % of the A side, the B side, or a combination of the A side and the B side. The reinforcing fibers may be present in an amount of about 3 wt % of the A side, the B side, or a combination of the A side and the B side.

[0103] The two-part system can include a hydrophobic silica. The hydrophobic silica can play a role in controlling viscosity (e.g., thickening), controlling thixotropy, enhancing hydrophobicity, or a combination thereof. The hydrophobic silica can be a fumed silica. The hydrophobic silica can be surface treated. For example, the hydrophobic silica can be a fumed silica surface treated with polydimethylsiloxane (hereinafter referred to as "PDMS") or hexamethyldisilazane (hereinafter referred to as "HMDZ"). The hydrophobic silica can be present as part of the A side, the B side, or both. Examples of suitable hydrophobic silicas can be those sold under the trade name Hydrophobic silica sold under the tradename CAB-O- Those sold as TS-530 and TS-720 are commercially available from Cabot Corporation in Boston, MA.

[0104] Hydrophobic silica may be present in an amount of about 0.25% by weight to about 15% by weight of the combination of the A side, the B side, or the A side and the B side. Hydrophobic silica may be present in an amount of about 0.1% by weight to about 4% by weight of the combination of the A side, the B side, or the A side and the B side. Hydrophobic silica may be present in an amount of about 1% by weight to about 3% by weight of the combination of the A side, the B side, or the A side and the B side. Hydrophobic silica may be present in an amount of about 1% by weight of the A side. Hydrophobic silica may be present in an amount of about 1% by weight to about 3% by weight of the B side. The ratio of the hydrophobic silica in the A side to the B side may be about 1:3 to about 3:1. The ratio of the hydrophobic silica in the A side to the B side may be about 1:2 to about 2:1.

[0105] The two-part system can include tabular alumina. Tabular alumina can serve to impart hardness, thermal shock resistance, mechanical shock resistance, high heat capacity, high electrical resistance, or any combination thereof to the reaction product. Tabular alumina can be present in the A side, the B side, or both. Tabular alumina can be alpha alpha alumina converted to its corundum form (i.e., crystalline alumina) and sintered, and can be provided as graded particles or powders. Tabular alumina can be graded (i.e., separated by size) to about 44 microns to about 4760 microns. Tabular alumina can be graded to about 44 microns.

[0106] The tabular alumina may be present in an amount of about 3 wt % to about 15 wt % of the A side, the B side, or a combination of both the A side and the B side. The tabular alumina may be present in an amount of about 4 wt % to about 12 wt % of the A side, the B side, or a combination of both the A side and the B side. The tabular alumina may be present in an amount of about 5 wt % of the A side. The tabular alumina may be present in an amount of about 10 wt % of the A side.

[0107] The two-part system may include one or more functional additives for improving one or more different properties of the composition. Examples of suitable functional additives may include antioxidants, antiozonants, UV absorbers, antistatic agents, colorants, coupling agents, curing agents, flame retardants, foaming agents, thermal stabilizers, impact modifiers, lubricants, plasticizers, preservatives, processing aids, stabilizers, etc., and any combination thereof.

[0108] The viscosity of the A side, the B side, or both can be high enough at about 23°C to prevent the two-part system from undesirably flowing into an area adjacent to the dispensed bead when dispensing the two-part system onto a workpiece, or to control the flow into an area adjacent to the dispensed bead when dispensing the two-part system (i.e., allowing a desired amount of flow). The viscosity of the A side, the B side, or both required to prevent undesirable flow or control flow can depend on the size of the beads being dispensed. For example, the thicker the beads of the two-part system being dispensed, the higher the viscosity required to prevent undesirable flow or control flow. The viscosity of the A side at 23°C can be about 20,000 cP to about 50,000 cP or even about 35,000 cP to about 45,000 cP. The viscosity of the A side and the B side at 23°C can be about 250,000 cP to about 400,000 cP. The viscosity of the A side at 10° C. can be about 280,000 cP to about 350,000 cP or even about 300,000 cP to about 325,000 cP. The viscosity of the B side at 23° C. can be about 20,000 cP to about 50,000 cP or even about 35,000 cP to about 45,000 cP. The viscosity of the B side at 10° C. can be about 130,000 cP to about 220,000 cP or even about 175,000 cP to about 195,000 cP.

[0109] After mixing the A and B sides, the two-part system can expand more than about 10%, more than about 50%, more than about 100%, less than about 300%, less than about 200%, or even less than about 150% based on the original volume of the two-part system. The two-part system can expand from about 50% to about 100% of the original volume of the two-part system.

[0110] The two-part system may be free of a curing agent (i.e., a typical curing agent), a curing accelerator, or both. Typical curing agents include Lewis bases (i.e., anionic catalysts), Lewis acids (i.e., cationic catalysts), UV catalysts, amines, anhydrides, phenols, thiols, or any combination thereof. Instead of the above-mentioned curing agents, the two-part system may be cured after a polymerization reaction between a phosphate ester catalyzed by phosphoric acid and an epoxy group, a hydroxyl group, or both. The two-part system may both cure and cause its expansion through chemical interactions between the phosphate ester and the metal carbonate. It has been found that the complexity of the formulation can be reduced by reducing the number of overall components (i.e., curing agent, curing accelerator, and blowing agent) using the curing and expansion system disclosed herein; however, achieving the desired expansion and curing time makes optimization more challenging.

[0111] Examples of formulations are shown in Table 1. These are examples where different amounts of ingredients such as DER732, epoxidized linseed oil, Silmer EPC-Di50 and Portland cement on the A side and P2O5 on the B side were investigated.

[0112] Table 1

[0113]

[0114] Table 2 illustrates some mechanical test results for the formulations shown in Table 1. Dry samples were prepared at ambient temperature and pressure. Underwater samples were prepared underwater and stored underwater prior to testing. Lap shear samples were prepared when both substrates were below the water line; the material was sprayed on one substrate and the second substrate was placed on top of it. They were taken out of the water one day before testing and kept in ambient conditions and then tested under conditions similar to the dry samples. Lap shear tests were performed on 2 mm thick Al 6061 with a bond line of 1 mm and an overlap of 25.4 mm × 25.4 mm. UW-69 showed better lap shear strength under dry conditions, UW-70 showed better lap shear strength under water, and UW-73 showed similar lap shear strength under dry conditions and underwater. Samples UW-70 and 73 cured much faster and were more rigid than sample UW-69. The shorter cure time is mainly due to the presence of P2O5 on the B side and more epoxidized linseed oil on the A side. The addition of P2O5 to the B side and the increase in epoxidized linseed oil on the A side both increased the lap shear strength after underwater cure compared to formulations without P2O5 and with less epoxidized linseed oil. The peel loads were higher for all three samples when underwater cured compared to dry cured conditions.

[0115] Table 2

[0116]

[0117] Figure 1 Stainless steel 304 lap shear strength under dry and underwater cure conditions is shown for UW-69, UW-70, and UW-73 formulations (from Table 1). Lap shear testing was performed based on the method specified in ASTM D 1002-10. Lap shear was performed on 2 mm thick stainless steel 304 with a bond line of 1 mm and an overlap of 25.4 mm x 25.4 mm. For all three samples, the underwater cure results were better than the dry cure results. Both the dry cure results and the underwater cure results for UW-69 were higher than those for UW-70 and UW-73.

[0118] Figure 2A and Figure 2BThe aging effect on the dry cured sample (2A) and the underwater cured sample (2B) before testing is shown. Lap shear testing was performed based on the method specified in ASTM D1002-10. Lap shear was performed on 2mm thick A16061, where the bond line was 1mm and the overlap was 25.4mm×25.4mm. For dry samples, the specimens were prepared and then stored for 3 days, 1 week, 2 weeks, or 3 weeks before testing. Underwater specimens were prepared underwater and then stored underwater for 3 days, 1 week, 2 weeks, 3 weeks, or 4 weeks. Before testing, the underwater specimens were removed and stored in the environment overnight. Over the course of three weeks, the dry curing results of all three formulations increased, but UW-69 had the largest increase. For underwater curing, the results of UW-70 increased within four weeks. UW-69 retained approximately 90% of the peak stress within four weeks, while UW-73 retained approximately 70%.

[0119] Figure 3 The lap shear strength of samples UW-69, UW-69a, and UW-69b under dry and underwater conditions are shown. Adding a small amount of Silmer EPC-Di50 (sample UW-69a) improved the underwater results. However, it reduced the dry lap shear strength. Adding a small amount of Portland cement (sample UW-69b) improved the dry cured lap shear compared to UW-69a, but reduced the lap shear after underwater curing. Lap shear testing was performed based on the method specified in ASTM D1002-10. Lap shear was performed on 2mm thick Al 6061 with a bond line of 1mm and an overlap of 25.4mm×25.4mm.

[0120] Table 3 shows the lap shear strength of samples UW-69, UW-70 and UW-73 cured in salt water and ice water conditions, respectively. The salt water samples were glued and stored in water / 3.5% NaCl for one week before testing. The ice water samples were glued in ice water and then stored in a 35°F refrigerator for one week before testing. Lap shear was performed on 2mm thick Al 6061 with a bond line of 1mm and an overlap of 25.4mm×25.4mm.

[0121] Table 3

[0122]

[0123] The two-part system can be provided as a side-by-side tube, a pail or a drum. The two-part system can be mixed before being dispensed on the workpiece. The two-part system can be applied to the workpiece via any suitable dispenser, and the two-part system is mixed by any suitable dispenser before being dispensed on the workpiece. For example, the two-part system can be dispensed on the workpiece via a static mixer, which is configured to deliver a mixed curable composition with a suitable mixing ratio, as described herein.

[0124] The two-part system can be used in any location where underwater repairs may be necessary. The two-part system can be used in any location that is in frequent contact with water. The two-part system can be used for marine applications. The system can be used in a variety of applications, such as various industrial manufacturing operations, and for a variety of construction purposes.

[0125] The present teachings provide a method that may include providing a two-part system that includes an A side (i.e., a first component) and a B side (i.e., a second component). The A side includes one or more epoxy resins, and the B side includes one or more phosphate esters and optionally phosphoric acid. The A side and the B side may be mixed to form a curable composition. The method may include the step of curing the curable composition at a temperature below 50°C to form a reaction product. The method may include the step of mixing the first component and the second component to form a reaction product. The method may include the following steps: wherein the reaction product of the first component and the second component is cured at a temperature below 50°C. The method may be carried out such that the A side includes one or more epoxy resins, metal carbonates, or both. The method may be carried out such that the B side includes one or more phosphate esters, phosphoric acid, or both. The method may be carried out such that the A side, the B side, or both have one or more additives.

[0126] Use of the teachings herein can produce a material that exhibits sufficient flame retardancy to meet one or more requirements for demonstrating flame retardancy (e.g., meeting the vertical burn and / or smoke density requirements (or some other requirements) as set forth in 14 C.FR §25.853 and 14 C.FR §25.856 (the Code of Federal Regulations for compartment interiors, including but not limited to 14 C.FR §25.853(a), and Appendix F and procedures referenced therein), all of which are incorporated by reference for all purposes.

[0127] As used herein, unless otherwise stated, the teachings contemplate that any member of a genus (list) may be excluded from that genus; and / or any member of a Markush group may be excluded from that group.

[0128] Unless otherwise stated, the numerical values ​​described herein include all numerical values ​​from lower values ​​to higher values, with an increment of 1 unit, provided that there is at least an interval of 2 units between any lower value and any higher value. As an example, if the amount of the value of a component, characteristic or process variable (such as temperature, pressure, time, etc.) is stated to be, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that the intermediate range values ​​(for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) are within the teaching of this specification. Similarly, separate intermediate values ​​are also within this teaching. For values ​​less than 1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only embodiments of specific intent, and all possible combinations of numerical values ​​between the lowest and highest values ​​listed should be considered to be the content clearly stated in a similar manner in this application. It can be seen that the teaching of the amount represented as "parts by weight" herein also contemplates the same range represented by weight percentage. Thus, language within a range of "at least "x" parts by weight" of a resulting composition also contemplates teaching of the same recited amount range of "x" percent by weight of the resulting composition.

[0129] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both ends of the range. Thus, "about 20 to 30" is intended to encompass "about 20 to about 30," including at least the specified endpoints. Unless otherwise stated, teachings with respect to the term "about" or "approximately" in combination with a numerical amount encompass teachings of the cited amount as well as approximate values ​​of the cited amount. For example, teachings of "about 100" encompass teachings of 100.

[0130] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The term "consisting essentially of" describing a combination shall include the identified elements, ingredients, components, or steps, as well as such other elements, ingredients, components, or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising" or "including" herein to describe a combination of elements, ingredients, components, or steps also contemplates embodiments consisting of or consisting essentially of the elements, ingredients, components, or steps.

[0131] Multiple elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step can be divided into separate multiple elements, ingredients, components or steps. The disclosure of "a" or "one" describing an element, ingredient, component or step is not intended to exclude additional elements, ingredients, components or steps.

[0132] It should be understood that the above description is intended to be illustrative and not restrictive. Many embodiments and many applications other than the examples provided will be apparent to those skilled in the art after reading the above description. Therefore, the scope of the present invention should not be determined with reference to the above description, but with reference to the full scope of equivalents given by the attached claims and such claims. The disclosures of all articles and references (including patent applications and publications) are incorporated by reference for all purposes. The omission of any aspect of the subject matter disclosed herein in the attached claims is not a waiver of rights to this subject matter, nor should it be considered that the inventor considers this subject matter to be a part of the disclosed inventive subject matter.

Claims

1. A two-part system, comprising: a) a first component, the first component include: - one or more epoxy resins; as well as - an epoxy functional material (compound) having an epoxy functionality greater than 4 and a viscosity less than 850 cps at 25°C as measured according to ASTM D-445; b) a second component comprising one or more phosphate esters; After mixing the first component and the second component at room temperature, a composition is formed, wherein: (i) having a peak lap shear stress after underwater curing of at least 7 MPa; and / or (ii) Contains or consists essentially of the following substances: (A) 40% to 85% by weight of the one or more epoxy resins, relative to the weight of the first component; preferably, wherein the one or more epoxy resins comprise or consist essentially of a liquid epoxy resin, an epoxy phenol novolac resin, an epoxy resin dissolved in xylene, or a combination thereof; (B) 0.5 wt % to 10 wt % of said epoxy-functional material, relative to the weight of said first component; preferably, wherein said epoxy-functional material comprises or consists essentially of epoxidized linseed oil; (C) 50% to 90% by weight of the one or more phosphate esters, relative to the weight of the second component; and (D) One or more additives in the first component and the second component.

2. The two-part system of claim 1, wherein after mixing the first component and the second component, the composition cures at a temperature of about 0°C to about 50°C.

3. A two-part system according to claim 1 or claim 2, wherein the first component comprises cement.

4. The two-part system according to any one of the preceding claims, wherein the first component comprises a silicone prepolymer.

5. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from cashew nut shell liquid (CNSL).

6. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from 2-ethylhexyl glycidyl ether.

7. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from phenyl glycidyl ether.

8. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from epoxidized p-tert-butylphenol.

9. The two-part system according to any one of the preceding claims, wherein the one or more phosphate esters comprises nonylphenol ethoxylated phosphate ester.

10. A two part system according to any one of the preceding claims wherein the epoxy functional material is epoxidised linseed oil.

11. The two-part system of claim 10, wherein the composition comprises one or more additives selected from the group consisting of core-shell polymers, metal carbonates, minerals, reinforcing fibers, hydrophobic silica, monomers, platy alumina, or any combination thereof.

12. The two-part system of claim 10, comprising calcium carbonate present in an amount of about 0.01 wt. % to about 10 wt. %, relative to the total weight of the two-part system.

13. The two-part system of any one of the preceding claims, comprising ultrafine calcium carbonate (about 1 micron average particle size), fine calcium carbonate (about 4 micron average particle size), medium fine calcium carbonate (about 22 micron average particle size), or any combination thereof.

14. A two-part system according to any one of the preceding claims, wherein one or both of the first component and the second component comprises wollastonite.

15. The two-part system of any one of claims 1 to 13, wherein one or both of the first component and the second component comprises fumed silica.

16. A two-part system according to any one of the preceding claims, wherein the second component comprises P 2 O 5 , polyphosphoric acid or a combination thereof.

17. The two-part system of any one of the preceding claims, wherein the second component comprises one or more of platy alumina, reinforcing fibers, hydrophobic silica, minerals, monomers, phosphoric acid, or any combination thereof.

18. The two-part system of any of the preceding claims, wherein the one or more epoxy resins or epoxy-functionalized resins comprise one or more liquid epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more phenoxy resins, one or more silane-modified epoxy resins, or any combination thereof.

19. The two-part system of any of the preceding claims, comprising one or more epoxy phenol novolac resins having a functionality of about 2 to about 3; epoxy phenol novolac resins having a functionality of about 3 to about 4; or both.

20. The two-part system according to any one of the preceding claims, comprising one or more epoxy phenol novolac resins present in an amount of about 30 wt % to about 70 wt %, preferably about 35 wt % to about 55 wt %, relative to the total weight of the first component.

21. A two-part system according to any one of the preceding claims, comprising one or more silicone prepolymers in an amount of at least 0.5 wt%, preferably at least 2 wt%, relative to the total weight of the first component.

22. The two-part system of any one of the preceding claims, wherein the composition cures at a temperature of from about 10°C to about 50°C.

23. The two-part system of any one of the preceding claims, wherein the composition cures at a temperature of about 15°C to about 25°C.

24. A two-part system according to any one of the preceding claims, wherein the composition cures in water.

25. The two-part system of any one of the preceding claims, wherein other than the phosphate ester, the two-part system is substantially free of a curing agent, a latent curing accelerator, or both.

26. A two-part system according to any one of the preceding claims, wherein the second component comprises P in an amount of about 1 wt. % to about 15 wt. %, preferably about 3 wt. % to about 10 wt. %, even more preferably about 5 wt. % to about 8 wt. %, relative to the total weight of the second component. 2 O 5 , polyphosphoric acid or a combination thereof.

27. A two-part system according to any of the preceding claims, wherein the first component comprises the epoxy-functional material in an amount of about 0.1 wt. % to about 15 wt. %, preferably about 0.4 wt. % to about 10 wt. %, even more preferably about 1 wt. % to about 7 wt. %, relative to the total weight of the first component.

28. A two-part system according to any one of the preceding claims, wherein the first component comprises epoxidized linseed oil in an amount of about 0.1 wt. % to about 15 wt. %, preferably about 0.4 wt. % to about 10 wt. %, even more preferably about 1 wt. % to about 7 wt. % relative to the total weight of the first component.

29. The two-part system according to any one of the preceding claims, wherein the first component comprises Portland cement in an amount of about 0.1 wt.% to about 10 wt.%, preferably about 0.5 wt.% to about 8 wt.%, even more preferably about 0.9 wt.% to about 5 wt.%, relative to the total weight of the first component.

30. A two-part system according to any one of the preceding claims, wherein the first component comprises an epoxy resin dissolved in xylene in an amount of about 0.5% to about 30% by weight, preferably about 2% to about 20% by weight, even more preferably about 5% to about 15% by weight, relative to the total weight of the first component.

31. The two-part system of any one of the preceding claims, wherein the composition comprises the first component and the second component in a ratio of about 5 parts by volume of the first component to about 1 part by volume of the second component.

32. The two-part system of any one of the preceding claims, wherein the composition comprises the first component and the second component in a ratio of about 4 parts by volume of the first component to about 1 part by volume of the second component.

33. The two-part system of any one of the preceding claims, wherein the composition comprises the first component and the second component in a ratio of about 3 parts by volume of the first component to about 1 part by volume of the second component.

34. A two-part system, comprising: (A) a liquid epoxy resin in a first component and an epoxy resin dissolved in xylene; (B) an epoxy-functional material comprising epoxidized linseed oil in the first component; (C) one or more phosphate esters in the second component; (D) P in the second component 2 O 5 , polyphosphoric acid or a combination thereof.

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