Enhanced light-cured CIPP vinyl esters compositions

Abstract

A series of innovative epoxy vinyl ester resin compositions specifically designed for Cured-In-Place Pipe (CIPP) applications, showcasing enhanced UV curing capabilities. These thickenable resin formulations incorporate an epoxy vinyl ester resin and a 1,3-dicarbonyl alkoxide complexes derived from group 13 elements (boron group). Engineered to exhibit accelerated curing, increased wall cure thickness, and optimal viscosity for saturating fiberglass liners, this invention finds applicability in rehabilitating sewer and force main pipelines through the CIPP technique, greatly improved over today's best available technologies

Description

[0001] ENHANCED LIGHT-CURED CIPP VINYL ESTERS COMPOSITIONS

[0002] CROSS REFERENCE TO RELATED APPLICATIONS

[0003]

[0001] This nonprovisional application claims the benefit of priority under 35 USC §119 to U.S.

[0004] Patent Application No. 63 / 562,917, filed on March 8, 2024, the entirety of which is incorporated herein by reference.

[0005] BACKGROUND OF THE INVENTION

[0006]

[0002] Field of the invention

[0007]

[0003] The invention pertains to the rehabilitation of underground pipelines using the Cured-In-

[0008] Place Pipe (CIPP) method, involving thermoset resins saturating a liner and cured through ultraviolet light and / or light-emitting diodes. Specifically, the invention focuses on the viscosity maturing technique and light curing of epoxy vinyl ester resin compositions.

[0009]

[0004] Description of the Background

[0010]

[0005] The CIPP method is employed for the restoration of gravity pipelines, including full- length lining or point repairs, as well as lateral connections of mainline pipes to residences or businesses. Additionally, it proves effective in rehabilitating sewer force mains and potable water pipelines. In prior art methods employing this technology, liners were cured under standard temperature and pressure (STP) conditions. However, the need for faster cure times led to the development of methods using hot water, steam, and, more recently, ultraviolet lights and light- emitting diodes.

[0011]

[0006] Existing light-cured liners typically consist of felt and / or fiberglass embedded in resin with a photoinitiator. Resins with thixotropic properties are used in certain prior art CIPP systems to prevent drain downs. However, existing CIPP systems utilizingfiberglass s liners commonly use low viscosity, “non-thixotropic” resins, which typically provide faster liner impregnation times and greater fiber saturation as compared with higher viscosity resins with thixotropic properties. To counter resin pooling in these prior art systems, then, thickening additives are commonly incorporated before liner impregnation, enhancing viscosity maturation and effective molecular weight. Known thickening agents generally comprise compounds based on Group 1 and 2 metals, or chemical thickening agents such as isocyanates.

[0012]

[0007] US Patent No. 4,347,343, to James L. Brewbaker (“Brewbaker”) discloses one such thickening agent utilized in the prior art to counter resin pooling and related issues in low viscosity resins. Brewbaker discloses a curable vinyl ester resin-based composition which uses a thickening agent comprising an acid functionalized oxyalkylene polymer. Unfortunately, commonly used thickening agents, like the one disclosed by Brewbaker, can cloud the resin and impact curing thickness.

[0013]

[0008] Moreover, chemical thickening agents such as isocyanates introduce health hazards for the employees producing and handling the C1PP liners, and may have environmental impacts as well.

[0014]

[0009] Therefore, an improved CIPP system with a higher viscosity resin, which does not suffer from the drawbacks of clouding, negative impacts on curing thickness, and health or environmental hazards would be advantageous.

[0015] SUMMARY OF THE INVENTION

[0016]

[0010] Accordingly, an object of the present invention is to provide a vinyl ester resin compositions with increased wall cure thickness.

[0017]

[0011] Another object of the invention is to provide vinyl ester resin compositions with faster curing properties.

[0012] Another object of the invention is to provide vinyl ester resin compositions with viscosity maturing properties for proper impregnation of a CIPP liner.

[0018]

[0013] Another object of the invention is to provide vinyl ester resin compositions as described above, but which do not provide any negative impacts on curing properties for a light-cured resin. Likewise, an object of the invention is to provide such a composition which includes or is ready to be mixed with a photoinitiator compound.

[0019]

[0014] Another object of this invention is to provide vinyl ester compositions with mechanical and physical properties suitable for relining sewer and force main pipelines.

[0020]

[0015] Other means for curing CIPP systems involve the use of peroxides and / or azo initiators.

[0021] Therefore, another object of the present invention is to provide a CIPP system which provides increased wall cure thickness, faster curing properties and / or viscosity maturing properties for proper impregnation of a CIPP liner which can be cured via peroxides, azo initiators, ultraviolet light or light-emitting diodes, such that it can be flexible to accommodate one or more available modalities in the field.

[0022]

[0016] Therefore, the present invention is a set of chemically modified vinyl ester and / or unsaturated polyester resin compositions suitable for the rehabilitation of gravity and force main sewers.

[0023]

[0017] In particular, the present invention is a set of chemically modified resins which are combined with a group 13 1,3-dicarbonyl alkoxide complex, the combination of which shows superior qualities for use in CIPP applications.

[0024]

[0018] In preferred embodiments, the metal complexes used according to the present invention are group 13 1,3-dicarbonyl alkoxide complexes derived from aluminum, such as (ethyl 3- oxobutyrato-O1 ’,O3)bis(propan-2-olato) aluminum.

[0019] The foregoing objects, features and attendant benefits of this invention will, in part, be pointed out with particularity and will become more readily appreciated as the same become better understood by reference to the following detailed description of a preferred embodiment and certain modifications thereof when taken in conjunction with the accompanying example formulations.

[0025] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026]

[0020] The present invention is a set of chemically modified resins which are combined with a group 13 1,3-dicarbonyl alkoxide complex , the combination of which shows superior qualities for use in CIPP applications.

[0027]

[0021] The present invention also includes a CIPP system including one or more specific types of chemically modified resins in combination with a group 13 1,3-dicarbonyl alkoxide complex, and a method of using same to rehabilitate fractured structures, and in particular potable water pipes, particularly underground and / or gravity pipelines.

[0028]

[0022] The present inventors have found that the use of a group 13 1,3-dicarbonyl alkoxide complex in the inventive CIPP system and method (in combination with a chemically modified resin of the disclosed type, as will be described) provides unexpectedly improved results in the nature of improvements of the desired properties for such resin systems in CIPP applications. In particular, the present inventors found that the innovative systems disclosed herein show unexpected improvement over prior art systems in terms of increased wall cure thickness, faster curing properties, low or no UV absorption in the same range as one or more desirable photoinitiators (further enhancing the curing properties), and viscosity properties which allow vastly improved impregnation of a CIPP liner. More specifically, the present inventors have found that, particularly in combination with a chemically modified resin as described herein and used in a CIPP application, the use of a group 13 1,3-dicarbonyl alkoxide complex provides desirable thickening qualities to the CIPP system. Moreover, the present inventors have found that the group 13 1,3-dicarbonyl alkoxide complex (and, in preferred embodiments, (Ethyl 3- oxobutyrato-O1 ’,03)bis(propan-2-olato) aluminum) does not impact the curing properties of the resin when used in combination with a photoinitiator and UV light, because the novel CIPP system does not absorb UV light in the range absorbed by the photoinitiator in order to initiate the cure.

[0029]

[0023] As used herein, the terms “group 13 1,3-dicarbonyl alkoxide complex”, “group thirteen

[0030] 1,3-dicarbonyl alkoxide complex", “group 13-based 1,3-dicarbonyl alkoxide complex”, and

[0031] “group thirteen-based 1,3-dicarbonyl alkoxide complex”, will all be understood to refer to any chemical complex based on boron, aluminum, gallium, or indium, etc., and in particular, to the p- keto ester complexes variety of the metals in group 13 (of the periodic table). In addition, dispersions of such metal complexes in white mineral oil, fatty acids esters and polyesters will be understood to provide similar efficacy and also fall under the definition of “group 13 1,3- dicarbonyl alkoxide complex" as used herein. In preferred embodiments, the group 13 1,3- dicafbonyl alkoxide complex used herein is capable of ligand exchange with hydroxyl, carboxyl, carboxylate, 1,3-dicarbonyl, 0-hydroxy ketone, and / or oxirane pendant functional groups. Other exemplary compounds which are potential alternatives within group 13 complexes are: 1 -ethoxy-

[0032] 3-oxobut-l-en-l-yl diisopropyl borate; Boronic acid; Triisopropyl borate; Acetylacetonate borate; Aluminum isopropoxide; Aluminum acetylacetonate; Gallium isopropoxide; Gallium acetate; Gallium (E)-l-ethoxy-3-oxobut-l-en-l-olate dipropan-2-olate; Indium(III) (E)-l-ethoxy- 3-oxobut-l-en-l-olate dipropan-2-olate; Indium isopropoxide; Indium acetate; and Indium acetylacetonate.

[0033]

[0024] Likewise, other references herein to Group 1, Group 2, and the like will be understood by a person having ordinary skill in the art to refer to the elements under the denoted group in the periodic table, or compounds containing same, as the case may be.

[0034]

[0025] Also as used herein, the term “chemically modified resin” will be understood to refer to one of the following: a standard vinyl ester resin (the product of an epoxy resin and either acrylic acid or methacrylic acid), an acid modified vinyl ester resin, or a vinyl ester resin which is blended with an acid-containing unsaturated polyester. More specifically, the term “acid modified vinyl ester resin” shall be understood to refer to a vinyl ester resin which has been modified by reaction with an acid or anhydride, which acid or anhydride may be selected from the (non-limiting) group comprising: maleic anhydride, fumaric acid, known dicarboxylic acids, succinic anhydride, succinic acid, itaconic acid, itaconic anhydride, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride and similar compounds, hi some embodiments, the acid modification is effected by blending the vinyl ester resin with an acid-containing unsaturated polyester resin. In particular, in preferred embodiments, the “acid modification” is the result of a reaction between the hydroxy groups present in the starting vinyl ester composition and the acid / anhydride moiety. In some embodiments, the vinyl ester resin is a bisphenol- A free derived vinyl ester. In preferred embodiments, the vinyl ester resin is Bisphenol-A vinyl ester resin. In preferred embodiments of the present invention where the vinyl ester resin is blended with an acid-containing unsaturated polyester resin, that unsaturated polyester resin is an Isophthalic neopentyl glycol derived resin. In other preferred embodiments, the vinyl ester resin is

[0035] Bisphenol-A-free vinyl ester resin.

[0036]

[0026] In other embodiments, the vinyl ester resin will be derived from sources such as

[0037] Bisphenol-F, Bisphenol-S, Resorcinol diglycidyl ether, Novolac, Neopentyl glycol diglycidyl ether, Cyclohexanedimethanol diglycidyl ether, Epoxidized soybean oil, Epoxidized fatty acids, among others.

[0038]

[0027] In preferred embodiments of the present invention, the vinyl ester resin contains hydroxy, carboxyl, carboxylate and / or oxirane pendant functional groups.

[0039]

[0028] Thus, the present invention is a resin system optimized for use in CIPP applications, comprising a chemically modified vinyl ester resin and a group 13 1 ,3-dicarbonyl alkoxide complex. In preferred embodiments, the resin system will also include a photoinitiator, such as

[0040] Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), or other Type 1 and 2 photoinitiators, which are known in the art. According to preferred embodiments, the method of using the present invention includes the steps of: (A) preparing the chemically modified vinyl ester resin; (B) providing the chemically modified vinyl ester resin at the job site separately from the group 13 1 ,3-dicarbonyl alkoxide complex; (C) mixing the group 13 1 ,3-dicarbonyl alkoxide complex with the chemically modified vinyl ester resin, to form a combined CIPP composition, immediately prior to liner impregnation; (D) impregnating the liner with the combined CIPP composition (E) fitting a fiberglass liner into the pipe or other component to be repaired; and (F) curing. In preferred embodiments, the curing is done via ultraviolet light.

[0041]

[0029] Also in preferred embodiments, the group 13 1 ,3-dicarbonyl alkoxide complex according to the present invention is (Ethyl 3-oxobutyrato-O1 ’,O3)bis(propan-2-olato) aluminum.

[0042] Preferred embodiments of the present invention advantageously utilize group 13 1 ,3-dicarbonyl alkoxide complexes derived from aluminum, including but not limited to (ethyl 3-oxobutyrato-

[0043] O1 *,O3)bis(propan-2-olato) aluminum. Also, in preferred embodiments of the present invention, the group 13 1,3-dicarbonyl alkoxide complex is present in the combined CIPP composition in a range of 1 -15wt%, or in a range of 1-9 wt%, or in a range of 3-7%, or in a range of 3-6%, by weight of the total combined CIPP composition. More specifically, the preferred wt% of group

[0044] 13 1,3-dicarbonyl alkoxide complex is between 2-9 wt% when the resin used in the inventive system is a Bisphenol-A vinyl ester resin, and 1-3 wt%, or 1.75 wt%, when the resin used in the inventive system is a combination of Bisphenol-A vinyl ester resin and Isophthalic neopentyl glycol resin.

[0045]

[0030] Vinyl ester resins are dissolved in a reactive diluent, which may be selected from a diluent of the types including, but not limited to, vinyl aromatic compounds such as: styrene, vinyl toluene, divinyl benzene, tert-butylstyrene, para-methylstyrene and similar. Other potential diluents include, mono-, di-, tri- and multi-functional acrylates and / or methacrylates such as: methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, butanediol methacrylate, butanediol acrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane tri(metb)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxlated glycerine tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and similar compounds.

[0031] The present inventors have found that favorable results have been achieved using a resin with the following characteristics: a maleic anhydride modified Bisphenol-A vinyl ester resin which is present in the combined CIPP composition in a range of 50-90%, or in the range of 63-

[0046] 67% by weight of the total components in the system.

[0047]

[0032] Additionally, the present inventors have found that the addition of isophthalic neopentyl glycol, in the range of 10-50 wt% of the total components in the system, or in the range of 18-22 wt% of the total combined CIPP composition, to the compositing comprising the above- identified maleic acid modified vinyl ester resin also enhances the surprisingly beneficial properties of the inventive system.

[0048]

[0033] The inventive resin system, as utilized as the herein-described combined CIPP composition, may also advantageously include one or more of the following components: stabilized styrene, Tripropylene glycol diacrylate, fumed silica, Thixotropic reagents (such as

[0049] B YK-R605), air release agents including but not limited to butadiene copolymer and Antifoam A

[0050] (a mixture of several siloxanes, the composition of which is known in the art). The inventors have also found that styrene-free resin systems are useful and beneficial for use in the present invention, particularly considering that the lack of styrene is generally advantageous for potable water applications.

[0051]

[0034] The present inventors have found that the inventive compounds, using group 13 1,3- dicarbonyl alkoxide complexes, overcome the drawbacks of the prior art by providing a thickened / thickenable resin, ideal for CIPP systems but also benefiting other applications, which does not provide a cloudy resin or produce health or environmental hazards for users or the surrounding area. Moreover, the present inventors have learned that the inventive formulations unexpectedly also exhibit superior characteristics, as compared with the prior art, in terms of the depth of through-cure (allowing the UV rays to penetrate deeper into the substrate when photoinitiated, during the curing process), resulting in improved mechanical performance of the final composite article, and faster cure processing time. Notably, the inventors have also found that the presently disclosed resin compositions unexpectedly provide fester thickening times upon application. All of the foregoing benefits represent improvements over the prior art

[0052]

[0035] Moreover, some of the potential alternatives, within group 13 complexes, disclosed above, are capable of being cured via one or more of peroxides, azo initiators, ultraviolet light or light-emitting diodes. Thus, the compound according to the disclosed invention could also be mixed with an operative quantity of peroxides and / or azo initiators, in addition to or as an alternative to photoinitiators. In one exemplary use case, it is known for certain compounds that peroxides provide a faster cure than photoinitiators. Therefore, in some preferred embodiments, the inventive compound includes both peroxides and photoinitiators. In that case, the inventive compound can advantageously provide enhanced qualities such as increased wall cure thickness, faster curing properties and / or viscosity maturing properties for proper impregnation of a CIPP liner, and advantageously do not absorb light in the same frequency range as the photoinitiator, such that the effectiveness of the photoinitiator is not diminished. Additionally, however, the presence of the peroxide in the inventive compound can then utilize the heat generated with the

[0053] UV-curing process to initiate decomposition of the peroxide to start a peroxide curing process, which may then provide a faster cure assuming the UV-curing process becomes sluggish.

[0054]

[0036] To illustrate the foregoing, the filllowing, non-limiting exemplary formulations are provided:

[0055]

[0037] Example 1: Thickenable vinyl ester formulation 1 was produced as follows. To a bisphenol A vinyl ester base in styrene the following ingredients were added: filmed silica (Aerosil 200HV), thixotropic reagents (BYK-R605), air release agents (butadiene copolymer and

[0056] Antifoam A), and styrene. The product is then thickened using a dispersion of (Ethyl 3- oxobutyrato-O1’, O3)bis(propan-2-olato) aluminum in an unsaturated polyester (80% active ingredient). The quantity of each component within the composition here described are shown in

[0057] Table 1 below. In general, Table 1 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0058]

[0038] In another exemplary embodiment, the formulation shown in Table 1 is utilized, wherein

[0059] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0060]

[0039] Example 2: Thickenable vinyl ester formulation 2 was produced as follows. To a bisphenol A vinyl ester base in styrene the following ingredients were added: air release agents

[0061] (butadiene copolymer), and styrene. The product is then thickened using a dispersion of (Ethyl 3- oxobutyrato-O1’, 03 )bis(propan-2-olato) aluminum in an unsaturated polyester (80% active ingredient). The quantity of each component within the composition here described are shown in

[0062] Table 2 below. In general, Table 2 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0063]

[0040] In another exemplary embodiment, the formulation shown in Table 2 is utilized, wherein

[0064] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0065]

[0041] Example 3: Thickenable vinyl ester formulation 3 was produced as follows. To a bisphenol A vinyl ester base in styrene the following ingredients were added: filmed silica

[0066] (Aerosil 200HV), thixotropic reagents (BYK-R605), air release agents (butadiene copolymer and

[0067] Antifoam A), and styrene. The product is then thickened using a dispersion of (Ethyl 3- oxobutyrato the ’,O3)bis(propan-2-olato) aluminum in an unsaturated polyester (80% active ingredient). The quantity of each component within the composition here described are shown in Table 3 below. In general, Table 3 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0068]

[0042] In another exemplary embodiment, the formulation shown in Table 3 is utilized, wherein

[0069] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0070]

[0043] Example 4: Thickenable vinyl ester formulation 4 was produced as follows. To a bisphenol A vinyl ester base in styrene the following ingredients were added: air release agents

[0071] (butadiene copolymer), and styrene. The product is then thickened using a dispersion of (Ethyl 3- oxobutyrato-O1 ’,03)bis(propan-2-olato) aluminum in an unsaturated polyester (80% active ingredient). The quantity of each component within the composition here described are shown in

[0072] Table 4 below. In general. Table 4 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0073]

[0044] In another exemplary embodiment, the formulation shown in Table 4 is utilized, wherein

[0074] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0075]

[0045] Example 5: Thickenable vinyl ester formulation 5 was produced as follows. To a bisphenol A vinyl ester base in tripropylene glycol diacrylate the following ingredients were added: filmed silica (Aerosil 200HV), thixotropic reagents (BYK-R605), air release agents

[0076] (butadiene copolymer and Antifoam A), and tripropylene glycol diacrylate. The product is then thickened using (Ethyl 3-oxobutyrato-O1,O3)bis(propan-2-olato) aluminum (100% active ingredient). The quantity of each component within the composition here described are shown in

[0077] Table 5 below. In general. Table 5 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0078]

[0046] In another exemplary embodiment, the formulation shown in Table 5 is utilized, wherein

[0079] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0047] Example 6: Thickenable vinyl ester formulation 6 was produced as follows. To a bisphenol A vinyl ester base in tripropylene glycol diacrylate the following ingredients were added: air release agents (butadiene copolymer), and tripropylene glycol diacrylate. The product is then thickened using (Ethyl 3-oxobutyrato-Ol’, 03 )bis(propan-2-olato) aluminum (100% active ingredient). The quantity of each component within the composition here described are shown in Table 6 below. In general, Table 6 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0080]

[0048] In another exemplary embodiment, the formulation shown in Table 6 is utilized, wherein

[0081] BAPO is replaced (in the same quantity ) with one of the known Type 1 or 2 photoinitiators.

[0082]

[0049] Example 7: Thickenable vinyl ester formulation 7 was produced as follows. To a maleic anhydride modified bisphenol A vinyl ester base in tripropylene glycol diacrylate the following ingredients were added: fumed silica (Aerosil 200HV), thixotropic reagents (BYK-R605), air release agents (butadiene copolymer and Antifoam A), and tripropylene glycol diacrylate. The product is then thickened using a dispersion of (Ethyl 3-oxobutyrato-Ol ’,O3)bis(propan-2-olato) aluminum in white mineral oil (85% active ingredient). The quantity of each component within the composition here described are shown in Table 7 below. In general, Table 7 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0083]

[0050] In another exemplary embodiment, the formulation shown in Table 7 is utilized, wherein

[0084] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0085]

[0051] Example 8: Thickenable vinyl ester formulation 8 was produced as follows. To a maleic anhydride modified bisphenol A vinyl ester base in tripropylene glycol diacrylate the following ingredients were added: air release agents (butadiene copolymer), and tripropylene glycol diacrylate. The product is then thickened using a dispersion of (Ethyl 3-oxobutyrato- O1 *,O3)bis(propan-2-olato) aluminum in white mineral oil (85% active ingredient). The quantity of each component within the composition here described are shown in Table 8 below. In general, Table 8 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0086]

[0052] In another exemplary embodiment, the formulation shown in Table 8 is utilized, wherein

[0087] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0088]

[0053] Example 9: Thickenable vinyl ester formulation 9 was produced as follows. To a maleic anhydride modified bisphenol A vinyl ester base in tripropylene glycol diacrylate the following ingredients were added: an isophthalic unsaturated polyester in tripropylene glycol diacrylate, firmed silica (Aerosil 200HV), thixotropic reagents (BYK-R605), air release agents (butadiene copolymer and Antifoam A), and tripropylene glycol diacrylate. The product is then thickened using a dispersion of (Ethyl 3-oxobutyrato-Ol’,O3)bis(propan-2-olato) aluminum in a mixture of fatty acids esters (85% active ingredient). The quantity of each component within the composition here described are shown in Table 9 below, In general, Table 9 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0089]

[0054] In another exemplary embodiment, the formulation shown in Table 9 is utilized, wherein

[0090] BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0091]

[0055] Example 10: Thickenable vinyl ester formulation 10 was produced as follows. To a maleic anhydride modified bisphenol A vinyl ester base in tripropylene glycol diacrylate the following ingredients were added: an isophthalic unsaturated polyester in tripropylene glycol diacrylate, air release agents (butadiene copolymer), and tripropylene glycol diacrylate. The product is then thickened using a dispersion of (Ethyl 3-oxobutyrato-Or,03)bis(propan-2-olato) aluminum in a mixture of fatty acids esters (85% active ingredient). The quantity of each component within the composition here described are shown in Table 10 below. In general,

[0092] Table 10 below illustrates the constituents of the comprehensive CIPP composition before the fiberglass impregnation process.

[0093]

[0056] In another exemplary embodiment, the formulation shown in Table 10 is utilized, wherein BAPO is replaced (in the same quantity) with one of the known Type 1 or 2 photoinitiators.

[0094]

[0057] Example Formulations

[0095] a) est were run by placing 18g of catalyzed resin in a test tube. The test tube is placed in a circulating 25 °C water jacket. A 300W UV bulb with 360-395nm emission range is placed 3” away from the water jacket. b) Gel time measures resin gelation between 25-35 °C (minutes); cure time measures resin cure from 35 °C to peak exotherm (minutes); the total time is the addition of the previous two measurement (minutes) and Exotherm in measured in degrees Celsius (°C).

[0096]

[0058] This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains. STATEMENT OF INDUSTRIAL APPLICABILITY

[0097]

[0059] The present invention relates to an improved resin for use in a Cured-In-Place Pipe

[0098] (CIPP) method, which is a method of repairing underground pipelines using a liner saturated with a resin. There is great industrial applicability in systems for repairing leaks or breaches in underground pipelines, as these structures are used to transmit potable water in municipal water delivery systems, among other applications. The invention relates to an improvement to the CIPP system, and in particular improvements to the resin component of this system, which enables it to have a faster cure time, enabling a more timely repair to a critical resource.

Claims

We claim:

1. A composition comprising: a resin and a group 13 1,3-dicarbonyl alkoxide complex, wherein said resin is selected from the group comprising a vinyl ester resin or a resin comprising a blend of a vinyl ester resin and an acid-containing unsaturated polyester resin.

2. The composition of claim 1, wherein said resin has been modified by reaction with an acid or anhydride.

3. The composition of claim 2, wherein said acid or anhydride is selected from the group comprising maleic anhydride, fumaric acid, known dicarboxylic acids, succinic anhydride, succinic acid, itaconic acid, itaconic anhydride, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride.

4. The composition of claim 2, wherein said resin is a blend of a vinyl ester resin and an acid-containing unsaturated polyester resin, and wherein said reaction is effected by blending the vinyl ester resin with an acid-containing unsaturated polyester resin.

5. The composition of claim 4, wherein said acid-containing unsaturated polyester resin is an Isophthalic neopentyl glycol derived resin.

6. The composition of claim 2, wherein said chemically modified resin is a Bisphenol-A vinyl ester resin.

7. The composition of claim 1, wherein said group 13 1,3-dicarbonyl alkoxide complex is a chemical complex based on boron, aluminum, gallium, and indium.

8. The composition of claim 7, wherein said group 13-based thickening is found as part of a dispersion in mineral oils, fatty acids and / or polyesters.

9. The composition of claim 1, wherein said group 13 1,3-dicarbonyl alkoxide complex is aP-keto ester complex based on a group 13 metal.

10. The composition of claim 1, wherein said 1,3-dicarbonyl is a chemical containing 1,3- diketones, p-keto esters, p-oxo aldehydes, P-hydroxy ketones and similar.

11. The composition of claim 1 , wherein said alkoxide is chemical of the following nature: methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, and / or the anion of any hydroxy containing organic compound.

12. The composition of claim 1, wherein said group 13 1,3-dicarbonyl alkoxide complex is(Ethyl 3-oxobutyrato-Ol ’,O3)bis(propan-2-olato) aluminum.

13. The composition of claim 1 wherein said resin is a vinyl ester resin containing hydroxyl, carboxyl, carboxylateand / or oxirane pendant functional groups.

14. The composition of claim 1 wherein said resin is a blend of a vinyl ester resin and an acid-containing unsaturated polyester resin, and wherein said acid-containing unsaturated polyester resin contains hydroxyl, carboxyl, carboxylate and / or oxirane pendant functional groups.

15. The composition of claim 1, wherein said group 13 1,3-dicarbonyl alkoxide complex is capable of ligand exchange with hydroxyl, carboxyl, carboxylate, 1 ,3 -dicarbonyl, oxo, p-keto esters and / or oxirane pendant functional groups.

16. The composition of claim 1, wherein the composition does not include styrene.

17. The composition of claim I, wherein said chemically modified resin is a Bisphenol- A- free vinyl ester resin.

18. The composition of claim 1, further comprising a photoiniator compound.

19. A method of repairing a pipe, the method comprising:(A) providing a chemically modified resin which includes a photoinitiator;(B) providing a group 13 1,3-dicarbonyl alkoxide complex;(C) mixing said group 13 1,3-dicarbonyl alkoxide complex with said chemically modified resin to form a combined CIPP composition, immediately prior to liner impregnation;(D) impregnating said liner with said combined CIPP composition;(E) fitting a fiberglass liner into said pipe; and(F) curing said liner including said combined CIPP composition.

20. The method of claim 19, wherein said chemically modified resin is a vinyl ester resin which has been modified by reaction with an acid or anhydride.

21. The method of claim 20, wherein said acid or anhydride is selected from the group comprising maleic anhydride, fumaric acid, known dicarboxylic acids, succinic anhydride, succinic acid, itaconic acid, itaconic anhydride, adipic acid, phthalic anhydride, isophthalic acid,terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride.

22. The method of claim 20, wherein said chemically modified resin is a Bisphenol-A vinyl ester resin.

23. The method of claim 20, wherein said chemically modified resin is a Bisphenol-A-free vinyl ester resin.

24. The method of claim 20, wherein said chemically modified resin is the result of blending a vinyl ester resin with an acid-containing unsaturated polyester resin.

25. The method of claim 24, wherein said acid-containing unsaturated polyester resin is anIsophthalic neopentyl glycol derived resin.

26. The method of claim 20, wherein said group 13 1,3-dicarbonyl alkoxide complex is a chemical complex based on boron, aluminum, gallium and indium.

27. The method of claim 20, wherein said group 13 1,3-dicarbonyl alkoxide complex is an β- keto ester complex based on a group 13 metal.

28. The method of claim 19, wherein said group 13 1,3-dicarbonyl alkoxide complex is(Ethyl 3-oxobutyrato-O1,03)bis(propan-2-olato) aluminum.

29. A system for use in a cured in place pipe (CIPP) application, the system comprising (A) a resin which has been modified by reaction with an acid or anhydride, which acid or anhydride is selected from the group comprising maleic anhydride, fumaric acid, known dicarboxylic acids, succinic anhydride, succinic acid, itaconic acid, itaconic anhydride, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalicanhydride, and trimellitic anhydride; and (B) a group 13 1,3-dicarbonyl alkoxide complex comprising an ester complex based on a group 13 metal.

30. The system of claim 29, wherein said resin is a combination of vinyl ester resin andIsophthalic neopentyl glycol resin.

31. The system of claim 29, wherein said vinyl ester resin is a maleic acid modifiedBisphenol-A vinyl ester resin, and wherein said isophthalic neopentyl glycol is present in the range of 10-50 wt% of the total components in the system.

32. The system of claim 29, wherein said maleic anhydride modified Bisphenol-A vinyl ester resin is present in a range of 50-90% of the total components in the system.

33. The system of claim 30, wherein said group 13 1 ,3-dicarbonyl alkoxide complex is present in a range of 1-9 wt% of the total components in the system.

34. The system of claim 29, wherein said resin is a vinyl ester resin, and wherein said group13 1,3-dicarbonyl alkoxide complex is present in a range of 2-9 wt% of the total components in the system.

35. The system of claim 29, wherein said resin is a combination of Bisphenol-A vinyl ester resin and Isophthalic neopentyl glycol resin, and wherein said group 13 1,3-dicarbonyl alkoxide complex is present in a range of 1-3 wt% of the total components in the system.