Epoxide-based compositions

Abstract

Epoxide-based compositions are disclosed that can be cured at temperatures below about 70° C. The compositions are liquid at ambient conditions and therefore can be used to repair the interior surfaces of pipelines. The epoxide-based compositions comprise at least one epoxide component (Component A) and at least one curing agent component (Component B): (A) an epoxide component including at least one phenyl glycidyl ether polyepoxide having at least two epoxide groups of oxirane structure in the molecule; and (B) A curing agent component containing a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms. The composition is suitable for use in potable water applications in cured-in-place pipe (CIPP).

Description

[Technical Field]

[0001] The present invention relates to curable epoxide-based compositions. More particularly, the present invention relates to curable epoxide-based compositions that are liquid under ambient conditions and have a relatively long pot life.

[0002] Background technology In some applications, it is preferred that the viscosity of the epoxy hardener not change radically over an extended period of time after combining the epoxide and hardener, which can facilitate subsequent steps depending on the intended application, such as coating, laminating, injecting, potting, or impregnating the composite composition containing the reinforced or non-reinforced components.

[0003] When the combination of the epoxide component and the polyamine-based hardener is left for an extended period of time, a reaction may occur, causing the viscosity of the composition to increase. Therefore, the composition has a maximum time during which it can be used in coating, laminating, pouring, potting, impregnation, etc. The period that begins when the composition is combined and ends when the viscosity of the combination increases to the point where it can no longer perform the desired work procedure is called the "pot life" or working life. In many applications, a longer pot life is a desirable characteristic to facilitate processing flexibility.

[0004] It is known in the art that mixed compositions containing a solid epoxide component and a similarly solid hardener component have a long pot life (or shelf life). This is because the initiation of curing depends on the thermal fusion of the two components. Also known are many semi-liquid compositions obtained by dispersing a solid hardener component in a liquid epoxide component. In this case, the hardener component is also solid, so the initiation of curing depends on the mixing of the two components by thermal fusion or mutual dissolution of the hardener components.

[0005] However, compositions containing solids have drawbacks due to the fact that at least one component is solid. More specifically, in the case of composite materials, such as fiber-reinforced composites containing a resin binder and fibers, the resin binder needs to penetrate into the fiber bundles. However, if a solid component is used, a filtering phenomenon occurs through the fibers, causing the binder components to separate, which can result in poor curing. The same applies when textiles or the like are used as reinforcing materials. Therefore, a liquid epoxide component and a liquid curing agent component are desirable as materials that can overcome these problems.

[0006] Another drawback of known compositions is that they have a relatively short pot life. Generally, compositions with a short pot life undergo rapid reaction and reach a cured state in a short time, whereas compositions with a long pot life require a long time to cure. As a result, there is a need in the art for liquid epoxide-based compositions that have a long pot life of several tens of hours and can be cured at relatively low temperatures (medium temperatures) below 100°C.

[0007] Such compositions, comprising an epoxide and a curing agent, both of which are liquid, allow for paint coatings to be applied to protect the interior surfaces of water supply pipes, sewer pipes, or other industrial liquid transport pipes, or gas supply pipes in outdoor structures, for example, by using organic or organic fibers or films, etc., to laminate protective linings that also function as pipe reinforcement. In particular, the compositions would be useful for repair work on the interior surfaces of pipes, etc., without excavating fluid or gas transport pipes already buried underground, such as those used in cured-in-place pipe (CIPP) technology.

[0008] Repair work on these buried pipes is usually carried out by setting the section between manholes as a single operation. The work procedure involves, in sequence, mechanically removing the old coating remaining on the inside of the pipe, washing with water, drying, coating with a resin component, spreading an inverted fiber or film using hot air or hot water, and maintaining a given temperature using hot water or hot air. When repairing using fiber or film, in short work options, even if the pot life of the composition is short, coating the inside of the pipe with a binder and spreading an inverted cylindrical fiber or film may be performed, but in long work options, it can take tens of hours.

[0009] There is a need in the art for composite systems that can be applied to the interior steel or concrete walls of pipes used to transport water or other fluid media for the repair of such pipes. Known compositions, such as unsaturated polyester / styrene polymers, cannot provide adequate working time (pot life), pose odor or toxicity issues from the chemicals used in the binder (e.g., mercaptans, acrylonitrile, isocyanates, styrene), or cannot be applied to multilayer and opaque films / composites due to the curing process (e.g., UV curing).

[0010] US Patent Application Publication No. 2010 / 0227981 discloses a composition comprising at least one phenyl glycidyl ether polyepoxide having at least one epoxide group of oxirane structure in the molecule and a curing agent component comprising a salt compound formed from an N-alkanol piperidine and a carboxylic acid, which can be used to repair water pipes at a curing temperature of less than 100°C, specifically 80°C.

[0011] For pipes carrying potable water, it is extremely important that there is no or minimal (less than 10 ppb) leaching of the hardener into the water. Described herein is the use of a salt of a hydrophobic tertiary amine and a hydrophobic carboxylic acid as a curing agent designed for the rehabilitation of potable water pipes. This combination of amine and carboxylic acid has been demonstrated to provide curing of epoxy resins at elevated temperatures (>55°C). Cured materials made with this curing agent and epoxy resin showed minimal (less than 10 ppb) leaching of the hardener in water at 25°C after 28 days.

[0012] The disclosures of the above-identified patents and patent applications are incorporated herein by reference.

[0013] Summary of the Invention The present invention solves problems associated with known compositions by providing compositions that can be cured at temperatures below about 80° C. (e.g., 65° C., about 55° C. to about 70° C., and in some cases about 62° C. to about 65° C.) The compositions of the present invention are liquid at ambient conditions and, therefore, can be used to repair the interior surfaces of pipelines (e.g., at a temperature of about 75° C., the uncured compositions of the present invention have a viscosity of about 1000 to about 2000 cP, about 1500 to about 2000 cP, and in some cases about 1000 to about 1200 cP).

[0014] The epoxide-based composition according to the present invention comprises at least one epoxide component (Component A) and at least one hardener component (Component B). In one aspect of the invention, the composition comprises: (A) an epoxide component comprising a phenyl glycidyl ether polyepoxide, and (B) A curing agent component includes a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms. The hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms has a water solubility of less than 0.1 g / L.

[0015] In another aspect of the present invention, the curable epoxide-based compositions of the present invention have the advantage that, even after mixing of the epoxy and hardener components, the composition can remain in an uncured state for an extended period of time, thereby allowing the composition to maintain a workable viscosity until use of the composition in the next step (or operation). For example, the compositions of the present invention can have a pot life of about 20 to about 30 hours at a temperature of about 25°C and 7 days or more at 5°C.

[0016] The compositions may be used with known epoxy diluents, such as monoglycidyl ethers, to modify the viscosity for ease of processing as desired, such as butyl glycidyl ether, phenyl glycidyl ether, dodecyl glycidyl ether, and the like.

[0017] Curing agent B may optionally be combined with a hindered polyetheramine co-curing agent (less than 50 wt. % relative to curing agent B) to increase the crosslink density and mechanical strength of the cured product. Additionally, if desired, small amounts of known epoxy cure accelerators (less than 10 wt. % relative to component B) may be blended into component B to further reduce cure time without compromising latency.

[0018] In a further aspect, the epoxide-based compositions of the present invention can remain uncured for extended periods of time after mixing the epoxide and hardener components, allowing subsequent processes such as coating, sandwiching, impregnation, and injection to be carried out slowly, and further allowing subsequent curing to occur within 3 hours at relatively low temperatures of 80° C. or less. This aspect of the present invention is useful for buried pipe rehabilitation and repair work.

[0019] In one aspect, the present invention provides an epoxide-based composition that, after mixing of the epoxide compound and the curing component, remains flowable (non-gelled) for an extended period of time (e.g., up to 24 hours at 25°C and for more than 7 days at 5°C) and ensures that the viscosity of the mixture does not exceed 10,000 cP within 16 hours, thereby facilitating subsequent application and spreading of the composition. The present invention also provides an epoxide-based composition that can be cured by using a heat medium such as hot water or hot air or other heating device in the medium temperature range (e.g., about 55 to about 80°C).

[0020] The present invention provides compositions that have a pot life of up to 24 hours at 25° C. and greater than 7 days when stored at 5° C. The compositions reflow when heated above 55° C., cure below 80° C., and provide good adhesion to concrete, steel fiberglass, and PVC substrates.

[0021] The salt compounds allow the compositions of the present invention to cure at relatively low temperatures (e.g., about 55 to about 80°C), whereas known compositions require cure temperatures of 80 to 150°C. As a result, the compositions of the present invention improve the usefulness of epoxide-based compositions containing the compositions of the present invention, especially when used in applications where high temperatures are difficult to obtain. In one embodiment of the present invention, the epoxide-based composition is applied to the interior surface of a pipe to repair or restore the pipe. The relatively low cure temperature of the epoxide-based composition allows the composition to be cured with a heat source (e.g., hot water or steam) located remotely from the epoxide-based composition. The hot water or steam may cool to temperatures below 70°C as it travels to the location of the composition to be cured, yet such temperatures are sufficient to cure the compositions of the present invention.

[0022] One aspect of the present invention is (A) an epoxide component including at least one phenyl glycidyl ether polyepoxide having at least two epoxide groups of oxirane structure in the molecule; and (B) an epoxide-based composition comprising a curing agent component including a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms. Preferably, the hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms has a water solubility of less than 0.1 g / L.

[0023] In one preferred embodiment, the amount of curing agent in component (B) is from about 1 to about 50 parts by weight per 100 parts by weight of epoxide component (A).

[0024] In another preferred embodiment, the epoxide component (A) further comprises an epoxide compound other than a phenyl glycidyl ether polyepoxide.

[0025] Preferably, the epoxide compound other than the phenyl glycidyl ether polyepoxide is at least one compound selected from the group consisting of glycidyl ethers, glycidyl esters, and glycidyl amines.

[0026] Preferably, the tertiary amine is selected from the group consisting of N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine and N,N-dimethylhexadecylamine. Preferably, the carboxylic acid is selected from the group consisting of decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, tall oil fatty acid, dimer acid and mixtures thereof.

[0027] MODE FOR CARRYING OUT THE INVENTION The epoxide-based compositions of the present invention can maintain a flowable condition for extended periods of time (e.g., a viscosity of less than 10,000 cP at 25°C for up to 24 hours) after mixing the epoxide compound and hardener components, with a viscosity not exceeding 10,000 cP within 16 hours. Furthermore, the epoxy compositions of the present invention can also be stored at 5°C for 7 days or longer without compromising shelf life (e.g., a viscosity of less than 10,000 cP at 25°C). The advantage of storing at low temperatures allows for flexibility in applying the hardener composition in a factory setting and then transporting the saturated liner to the job site for use with the CIPP. The liner is expected to be flexible when inserted into underground pipes during renovation.

[0028] Furthermore, the epoxide-based composition can be cured at medium temperatures (for example, from about 55°C to about 80°C) using a heat transfer medium such as hot water or hot air. Therefore, the epoxide-based composition according to the present invention can be used in repairing buried pipes that serve as conduits for various fluids.

[0029] Additionally, the epoxide-based compositions of the present invention are useful in remediation work that is performed without digging up buried pipes.

[0030] The present invention will be described in detail below. In the following description, "%" and "parts" that represent quantitative proportions or ratios are based on mass unless otherwise specified.

[0031] One aspect of the present invention is an epoxide-based composition comprising an epoxide component (component A) and a curing agent component (component B), wherein the epoxide component comprises a phenyl glycidyl ether-based polyepoxide having at least two epoxide groups with an oxirane structure in the molecule, and the curing agent component comprises a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms. Preferably, the hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms has a water solubility of less than 0.1 g / L.

[0032] Preferably, the hydrophobic tertiary amine is selected from the group consisting of N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-diethyldecylamine, N,N-diethylundecylamine, N,N-diethyldodecylamine, N,N-diethyltridecylamine, N,N-diethyltetradecylamine, N,N-diethylpentadecylamine, N,N-diethylhexadecylamine, N,N-diethylheptadecylamine, N,N-diethyloctadecylamine and N,N-diethylnonadecylamine.

[0033] Preferably, the carboxylic acid is selected from the group consisting of decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, tall oil fatty acid, dimer acid, and mixtures thereof.

[0034] Preferably, the epoxide component comprises at least one compound selected from the group consisting of aromatic diglycidyl ethers and glycidyl ethers. In a preferred embodiment, the epoxide component comprises a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F, or a combination thereof.

[0035] In one preferred embodiment, the epoxide component (A) further comprises an epoxide compound other than a phenyl glycidyl ether polyepoxide.

[0036] Preferably, the epoxide compound other than the phenyl glycidyl ether polyepoxide comprises at least one compound selected from the group consisting of glycidyl ethers, glycidyl esters, and glycidyl amines.

[0037] Preferably, the amount of the epoxide component can range from about 70 to less than 100% by weight of the epoxide-based composition, from about 85 to about 60% by weight of the epoxide-based composition, and in some cases from about 80 to about 90% by weight of the epoxide-based composition. Preferably, the hardener component can range from about 5 to about 30% by weight of the epoxide-based composition, from about 40 to about 20% by weight of the epoxide-based composition, and in some cases from about 20 to about 10% by weight of the epoxide-based composition.

[0038] In another preferred embodiment, the curative component (B) further comprises a hindered polyetheramine co-curative.

[0039] In another preferred embodiment, the epoxide-based composition further comprises an epoxy curing accelerator selected from the group consisting of 1-methylimidazole, 2-methylimidazole, tris(dimethylaminomethyl)phenol, and dimethylaminomethylphenol. The epoxy curing accelerator is preferably blended into the curing agent component (B).

[0040] In another preferred embodiment, the epoxide-based composition further comprises a diluent selected from the group consisting of butyl glycidyl ether, phenyl glycidyl ether, dodecyl glycidyl ether, and the like.

[0041] In a preferred embodiment, the amount of curing agent component (B) is from about 1 to about 50 parts by weight per 100 parts by weight of epoxide component (A). In another preferred embodiment, the amount of curing agent component (B) is from about 5 to about 20 parts by weight per 100 parts by weight of epoxide component (A). In another preferred embodiment, the amount of curing agent component (B) is from about 10 to about 30 parts by weight per 100 parts by weight of epoxide component (A).

[0042] Preferably, the epoxide component and the hardener component can be combined by using any suitable equipment and methods, such as mixing, stirring, pumping, among other equipment and methods known in the art.

[0043] Preferably, the salt of the curing agent can be obtained by reacting an amine with a carboxylic acid for 10 minutes to 6 hours at less than 80° C. Preferably, the molar ratio of amine to carboxylic acid is about 1:1.

[0044] In a preferred embodiment, the salt of the mixture ranges from 5 to 40% by weight of the composition.

[0045] The curable epoxide-based compositions disclosed herein can be used in potable water applications in cured-in-place pipe (CIPP).

[0046] The epoxide-based composition according to the present invention may have the following properties (1) to (3).

[0047] Characteristic 1 Under the conditions used in the examples, the viscosity of the epoxide-based compositions according to the present invention stored at 25°C for 24 hours or less and at 5°C for 7 days is less than 10,000 cP. Viscosity is determined using a Brookfield viscometer (Brookfield HT-2DB). A disposable aluminum spindle (Brookfield SC4-27D) is inserted into the chamber containing the curing agent mixture, and the viscometer (Brookfield RVDV-II+Pro) is started to collect data points at a rate of 1 / min according to standard test procedures.

[0048] Characteristic 2 The epoxy-based composition of the present invention can be cured within about 3 hours at temperatures below about 75°C to a hard, non-sticky feel. The curing temperature and time are inversely proportional, in that a longer curing time allows for a lower curing temperature. The curing temperature can range from about 55°C to about 80°C, from about 65°C to about 70°C, or in some cases, from about 60°C to about 65°C. The curing time can range from about 1 hour to about 3 hours, from about 2 hours to about 3 hours, or in some cases, from about 3 hours to about 4 hours.

[0049] Characteristic 3 The epoxy-based composition of the present invention can cure in the presence of at least 1% by weight of water at temperatures below 75°C within 3 hours and achieve a hard, non-sticky feel. The composition of the present invention can be cured in an environment containing about 2% to about 5%, about 3% to about 5%, and in some cases about 4% to about 8% water.

[0050] The epoxide component (A) of the composition of the present invention comprises a phenyl glycidyl ether epoxide having multiple oxirane structures in the molecule and reactive with amines, examples of which may include aromatic diglycidyl ethers obtained by reacting a diphenol such as bisphenol A, bisphenol F, bisphenol AD, tetramethylbisphenol A, tetramethylbisphenol F, or biphenyl with epichlorohydrin; glycidyl ethers obtained by reacting a novolak such as phenol novolak, cresol novolak, ethylphenol novolak, propylphenol novolak, butylphenol novolak, pentylphenol novolak, octylphenol novolak, or nonylphenol novolak with epichlorohydrin; and glycidyl ethers obtained by reacting a polyhydric phenol such as catechol, resorcinol, trihydroxybiphenyl, dihydroxybenzophenone, bisresorcinol, hydroquinone, tris(hydroxyphenyl)methane, tetrakis(hydroxyphenyl)ethane, or bisphenol with epichlorohydrin; and mixtures thereof.

[0051] Among the above epoxy compounds, preferable results can be obtained by using diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, or a combination thereof.

[0052] Examples of epoxides that can be used in combination with the phenyl glycidyl ether epoxides can include at least one member selected from at least one of the following groups: (1) Polyglycidyl ethers prepared by reacting aliphatic polyhydric alcohols such as glycol, neopentyl alcohol, ethylene glycol, propylene glycol, tetramethylene glycol, hexane glycol, polyethylene glycol, or polypropylene glycol with epichlorohydrin; (2) Glycidyl ether esters produced by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; (3) Polyglycidyl esters produced by reacting polycarboxylic acids such as phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydroxyphthalic acid, hexahydroxyphthalic acid, endomethylenetetrahydroxyphthalic acid, endomethylenehexahydroxyphthalic acid, trimellitic acid, dimer acid, or polymerized fatty acid with epichlorohydrin; (4) diglycidyl amino esters produced by reacting aminobenzoic acid with epichlorohydrin; and (5) Polyglycidylamines produced by reacting aniline, toluidine, m-xylylenediamine, 1,2-diaminocyclohexane, 4,4-diaminodiphenyl ether, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenyl sulfone, hydantoin, alkylhydantoin, or cyanuric acid with epichlorohydrin.

[0053] The hardener component (Component B) comprises a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms. The hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms has a water solubility of less than 0.1 g / L.

[0054] Any suitable tertiary amine can be used to make the aforementioned salts, but examples of preferred suitable tertiary amines are N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-diethyldecylamine, N,N-diethylundecylamine, N,N-diethyldodecylamine, N,N-diethyltridecylamine, N,N-diethyltetradecylamine, and N,N-diethylpentadecylamine. The tertiary amines are selected from the group consisting of N,N-diethylhexadecylamine, N,N-diethylheptadecylamine, N,N-diethyloctadecylamine and N,N-diethylnonadecylamine. Any other tertiary amines having the same or mixed alkyl groups with a hydrophobic alkyl chain (12 to 20 carbon atoms) are also suitable.

[0055] Preferably, in one embodiment, the carboxylic acid of the tertiary amine salt as the curing agent component of the present invention is selected from the group consisting of decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, tall oil fatty acid, dimer acid, and mixtures thereof.

[0056] Preferably, the salt can be formed by reacting the amine with the carboxylic acid for about 10 minutes to about 6 hours at less than 80° C. The molar ratio of amine to carboxylic acid is about 1:1, and can range from about 0.8 molar equivalents to about 1.0 molar equivalents, from about 0.9 molar equivalents to about 1.0 molar equivalents, and in some cases from about 1.0 molar equivalents to about 1.5 molar equivalents.

[0057] Preferably, component B of the epoxide-based compositions of the present invention can comprise from about 0.8 to about 1.2, from about 1.1 to about 1.2, and in some cases from about 1.0 to about 1.5 equivalents of carboxylic acid of component B per mole of hydrophobic tertiary amine.

[0058] The amount of curing agent component (B) can be in the range of about 1 to about 50 parts by weight, or about 5 to about 20 parts by weight, or about 10 to about 30 parts by weight per 100 parts by weight of polyepoxide component (A). If the amount of component B is less than the above range, a very long pot life after mixing component (A) and component (B) can be expected, but subsequent curing may require a long time, which is not practical. Conversely, if the amount of curing agent component (B) is combined in an amount exceeding the above range, curing after mixing component (A) and component (B) may proceed quickly, but the pot life required for operation may be shortened, which is generally not practical.

[0059] The composition of the present invention may also contain, if desired, at least one of a plasticizer, a filler, a colorant, an extender, a pigment, organic or inorganic fibers, a silicone to improve adhesion to the pipe body, a titanate or aluminum coupling agent, a thixotropic agent, etc. The amount may range from about 10% to about 20% by weight, from about 10% to about 12% by weight, or in some cases from about 18% to about 20% by weight of the epoxide-based composition.

[0060] Preferably, the compositions can be used with known epoxy diluents, such as monoglycidyl ethers, to modify the viscosity for ease of processing as desired, such as butyl glycidyl ether, phenyl glycidyl ether, dodecyl glycidyl ether, and the like.

[0061] Preferably, in one embodiment, curing agent B may optionally be combined with a small amount of a hindered polyetheramine (less than 50% by weight, based on B) to enhance the crosslink density and mechanical strength of the cured product. Preferred hindered polyetheramines include Jeffamine D230, Jeffamine T400, and Jeffamine T403, available from Huntsmann Corporation. Preferably, in a further embodiment, a small amount of a known epoxy cure accelerator (less than 10% by weight, based on B) may also be blended into component B, if necessary, to further shorten the cure time without compromising the waiting time. Preferably, the epoxy cure accelerator is selected from the group consisting of imidazoles, such as 1-methylimidazole, 2-methylimidazole, and tertiary amine-substituted phenols, such as tris(dimethylaminomethyl)phenol (Ancamine K-54, available from Evonik Corp.) and dimethylaminomethylphenol (Ancamine 1110, available from Evonik Corp.).

[0062] The following examples are provided to illustrate certain aspects of the present invention and are not intended to limit the scope of the appended claims.

[0063] The following invention relates to the following aspects. <1> (A) an epoxide component including at least one phenyl glycidyl ether polyepoxide having at least two epoxide groups of oxirane structure in the molecule; and (B) a curing agent component comprising a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms; 1. An epoxide-based composition comprising: <2> the hydrophobic tertiary amine is selected from the group consisting of N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-diethyldecylamine, N,N-diethylundecylamine, N,N-diethyldodecylamine, N,N-diethyltridecylamine, N,N-diethyltetradecylamine, N,N-diethylpentadecylamine, N,N-diethylhexadecylamine, N,N-diethylheptadecylamine, N,N-diethyloctadecylamine, and N,N-diethylnonadecylamine; <1> The composition described in <3> an embodiment in which the carboxylic acid is selected from the group consisting of decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, tall oil fatty acid, dimer acid, and mixtures thereof; <1> or <2> The composition described in <4> an embodiment in which the epoxide component comprises at least one compound selected from the group consisting of aromatic diglycidyl ethers and glycidyl ethers; <1> from <3> The composition according to any one of the preceding claims. <5>

[0023] The embodiment in which the epoxide component comprises a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F, or a combination thereof. <4> The composition described in <6> The embodiment in which the epoxide component (A) further comprises an epoxide compound other than a phenyl glycidyl ether polyepoxide. <1> from <5> The composition according to any one of the preceding claims. <7> an embodiment in which the epoxide compound other than phenyl glycidyl ether polyepoxide comprises at least one compound selected from the group consisting of glycidyl ethers, glycidyl esters, and glycidyl amines; <6> The composition described in <8> an embodiment in which the curative component further comprises a hindered polyetheramine co-curative; <1> from <7> The composition according to any one of the preceding claims. <9> an embodiment further comprising an epoxy cure accelerator selected from the group consisting of 1-methylimidazole, 2-methylimidazole, tris(dimethylaminomethyl)phenol, and dimethylaminomethylphenol. <8> The composition described in <10> an embodiment further comprising a diluent selected from the group consisting of butyl glycidyl ether, phenyl glycidyl ether, dodecyl glycidyl ether, and the like. <1> from <9> The composition according to any one of the preceding claims. <11> the amount of curing agent component (B) is from about 1 to about 50 parts by weight per 100 parts by weight of epoxide component (A); <1> from <10> The composition according to any one of the preceding claims. <12> In some embodiments, the salt of the mixture is in the range of 5 to 40% by weight of the composition. <1> from <10> The composition according to any one of the preceding claims. <13> Aspects of potable water applications with cured-in-place pipe <1> from <12> Use of the composition according to any one of the preceding claims.

[0064] Example Example 1: General procedure for preparing hardeners. The tertiary amine (1 mole) was charged to a three-necked round-bottom flask equipped with an overhead mechanical stirrer, nitrogen inlet, and thermocouple. The acid (1 mole relative to the amine) was added slowly to maintain the temperature below 80°C. If the acid is a solid, it is first melted and added to the amine in the liquid state.

[0065] Example 2: Amine Curing Agent Wait Time The curing agent is mixed with 100 g of bis-phenol A diglycidyl ether (EPON 828) at the specified loading level using a spatula in a 200 mL glass jar. The material is allowed to rest for a set time before testing. 15 g of this material is transferred to a disposable aluminum chamber (Brookfield HT-2DB). A disposable aluminum spindle (Brookfield SC4-27D) is inserted into the chamber containing the curing agent mixture, and the Start viscometer (Brookfield RVDV-II+Pro) is started to collect data points at a rate of 1 / min. If the viscosity is less than 10,000 cP at 25°C, the material is still flowable. Measurements were performed on the mixture after 24 hours at 25°C and 7 days at 5°C. The results are shown in Table 1.

[0066] Example 3: Viscosity and pot life tests at 65°C The curing agent is mixed with 100 g of bis-phenol A diglycidyl ether (EPON 828) at the specified loading using a spatula in a 200 mL glass jar. The material is stored at 5 °C for 7 days before testing. 15 g of this material is transferred to a disposable aluminum chamber (Brookfield HT-2DB). A disposable aluminum spindle (Brookfield SC4-27D) is inserted into the heated chamber at 65 °C containing the curing agent mixture, and a Start viscometer (Brookfield RVDV-II+ Pro) is started to collect data points at a rate of 1 / min. The initial viscosity and pot life (time to 10,000 °C) are recorded (Table 2).

[0067] Example 4: Testing Procedure for Hardeners with Epoxy Resins at 75°C The hardener was mixed with 100 g of bis-phenol A diglycidyl ether (EPON 828) at the specified loading in a 200 mL glass jar using a spatula. Packs were prepared from this mixture by transferring the hardener and epoxy resin mixture (approximately 5-7 g) to a 2 oz metal container. Two packs were prepared: one with water and one without. In the former, a small amount of water (approximately 2 g) was applied to one pack, but not enough to completely cover the entire surface. The packs were placed in a 75°C oven for 2 hours or until hardened. The hardening time and surface characteristics of the cooled packs were recorded, and tackiness, glassiness, and entrained air were determined by visual observation and contact hardness (Table 2).

[0068] [Table 1]

[0069] [Table 2]

[0070] Example 5: Simulated cure-in-place pipe application. To understand the applicability of the hardener in cured-in-place pipe (CIPP) applications, the following experiments were performed.

[0071] Hardener (50 g) (a 90:10 blend of N,N-dimethylhexadecylamine dodecanoate and Jeffamine D230) was mixed with 500 g of a standard DGEBA-type liquid epoxy resin with an EEW of 190 at ambient conditions. The mixed mass was sufficient to wet a commercially available, foot-long cylindrical felt measuring 4 inches in diameter, containing polyester fiber and a polyethylene lining. The mixed mass was applied to the felt by manually pouring the mixture onto the felt until it was completely saturated. This type of felt is commonly used for underground pipe repair.

[0072] The mixed mass was applied uniformly to the interior of a felt, and the felt was stored at 5°C for 7 days to confirm the product's storage stability. After 7 days, the felt was removed from storage at 5°C and equilibrated at 25°C for 24 hours. The felt appeared soft, and the mixed material was still tacky, making the felt soft enough for further processing. The saturated felt was then baked in an oven at 65°C for 2 hours. After cooling, the felt was very stiff, and the cured epoxy matrix exhibited an acceptable flexural modulus (>300,000 psi) required by industry. Flexural modulus was determined according to ASTM D-790.

[0073] While the present invention has been described with reference to particular aspects and embodiments, those skilled in the art will recognize that various combinations and modifications can be made and equivalents can be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is not intended that the invention be limited to the particular aspects or embodiments disclosed for carrying out this invention, but rather that the invention will include all aspects or embodiments falling within the scope of the appended claims.

Claims

1. (A) an epoxide component including at least one phenyl glycidyl ether polyepoxide having at least two epoxide groups of oxirane structure in the molecule; and (B) a curing agent component comprising a salt compound formed from a hydrophobic tertiary amine having an alkyl chain of 10 to 20 carbon atoms and a carboxylic acid having an alkyl chain of 10 to 40 carbon atoms; 1. An epoxide-based composition comprising:

2. 2. The composition of claim 1, wherein the hydrophobic tertiary amine is selected from the group consisting of N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-diethyldecylamine, N,N-diethylundecylamine, N,N-diethyldodecylamine, N,N-diethyltridecylamine, N,N-diethyltetradecylamine, N,N-diethylpentadecylamine, N,N-diethylhexadecylamine, N,N-diethylheptadecylamine, N,N-diethyloctadecylamine, and N,N-diethylnonadecylamine.

3. 3. The composition of claim 1 or 2, wherein the carboxylic acid is selected from the group consisting of decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, tall oil fatty acid, dimer acid, and mixtures thereof.

4. 4. The composition of claim 1, wherein the epoxide component comprises at least one compound selected from the group consisting of aromatic diglycidyl ethers and glycidyl ethers.

5. The composition of claim 4 , wherein the epoxide component comprises a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F, or a combination thereof.

6. 6. The composition of claim 1, wherein the epoxide component (A) further comprises an epoxide compound other than a phenyl glycidyl ether polyepoxide.

7. 7. The composition of claim 6, wherein the epoxide compound other than phenyl glycidyl ether polyepoxide comprises at least one compound selected from the group consisting of glycidyl ethers, glycidyl esters, and glycidyl amines.

8. 8. The composition of any one of claims 1 to 7, wherein the curative component further comprises a hindered polyetheramine co-curative.

9. 9. The composition of claim 8, further comprising an epoxy cure accelerator selected from the group consisting of 1-methylimidazole, 2-methylimidazole, tris(dimethylaminomethyl)phenol, and dimethylaminomethylphenol.

10. 10. The composition of any one of claims 1 to 9, further comprising a diluent selected from the group consisting of butyl glycidyl ether, phenyl glycidyl ether, dodecyl glycidyl ether, and the like.

11. 11. The composition of any one of claims 1 to 10, wherein the amount of the hardener component (B) is from about 1 to about 50 parts by weight per 100 parts by weight of the epoxide component (A).

12. 11. A composition according to any one of claims 1 to 10, wherein the salt of the mixture is in the range of 5 to 40% by weight of the composition.

13. 13. Use of a composition according to any one of claims 1 to 12 in cured-in-place pipes in potable water applications.

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