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WO2020050858A1 - Composition durcissable pour tuyaux durcis en place - Google Patents

Composition durcissable pour tuyaux durcis en place Download PDF

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Publication number
WO2020050858A1
WO2020050858A1 PCT/US2018/050008 US2018050008W WO2020050858A1 WO 2020050858 A1 WO2020050858 A1 WO 2020050858A1 US 2018050008 W US2018050008 W US 2018050008W WO 2020050858 A1 WO2020050858 A1 WO 2020050858A1
Authority
WO
WIPO (PCT)
Prior art keywords
curable composition
curing agents
weight percentage
resin
curing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2018/050008
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English (en)
Inventor
Richard E. NAWRACAJ
Gabriel URBIETA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Intellectual Property Resources Inc
Original Assignee
Intellectual Property Resources Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Intellectual Property Resources Inc filed Critical Intellectual Property Resources Inc
Priority to CA3111761A priority Critical patent/CA3111761A1/fr
Priority to JP2021512921A priority patent/JP7281222B2/ja
Priority to PCT/US2018/050008 priority patent/WO2020050858A1/fr
Priority to AU2018440151A priority patent/AU2018440151B2/en
Priority to EP18789272.4A priority patent/EP3847204A1/fr
Priority to MX2021002470A priority patent/MX2021002470A/es
Publication of WO2020050858A1 publication Critical patent/WO2020050858A1/fr
Anticipated expiration legal-status Critical
Priority to JP2023076640A priority patent/JP2023113624A/ja
Priority to AU2024204145A priority patent/AU2024204145A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C08G59/685—Carboxylates

Definitions

  • Curable compositions comprising an epoxy resin and a curing agent are well known in the art.
  • One common application for curable compositions is in the process of repairing existing pipelines (e.g., sewer or chemical pipelines). During this process, a curable composition filled liner is inserted or pulled into a damaged pipe. Once in place, the curable composition is cured with a hot water bladder or steam to form a tight-fitting replacement pipe. The resulting product, deemed a cured-in-place pipe, allows for seamless repair of a pipe with little to no excavation necessary, thereby making the process more cost effective than the alternative methods.
  • the curable composition For a curable composition to be adequately applied to cured-in-place applications, the curable composition must (i) have a sufficient latency period (i.e., time to form a gel) to be manageable while inserting into a damaged pipe, (ii) have enough structural integrity to fill the pipe and maintain conformity, and (iii) efficiently cure at temperatures compatible with a hot water bladder or steam.
  • composition with desirable qualities include changing the structure of the epoxy resin or the curing agent, adding a diluent to reduce viscosity and increase latency periods, and adding an accelerator to reduce curing times.
  • curable compositions provide inadequate results for one or more of the desirable qualities (i), (ii), and (iii).
  • economic production is also needed.
  • conventional curable compositions typically require high levels of curing agent or accelerator to efficiently cure at temperatures compatible with a hot water bladder or steam, or require a diluent to reduce viscosity and have a sufficient latency period (i.e., time to form a gel) to be manageable while inserting into a damaged pipe.
  • Such additional components increase costs associated with materials and equipment necessary for production of the curable composition.
  • the invention provides a curable composition
  • a curable composition comprising, consisting essentially of, or consisting of, (a) a resin comprising 4,4’-isopropylidenedi phenol -epi chi orohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • the invention further provides a curable composition
  • a curable composition comprising, consisting essentially of, or consisting of, (a) a resin comprising 4,4’-isopropylidenediphenol- epichlorohydrin copolymer and (b) one or more curing agents wherein at least one of the one or more curing agents is of Formula (II):
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group may be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • the invention also provides a method of curing a cured-in-place liner, wherein the method comprises: (i) placing the cured-in-place liner in a pipe and (ii) heating the cured-in- place liner, wherein the cured-in-place liner contains a curable composition comprising, consisting essentially of, or consisting of, (a) a resin comprising 4,4’-isopropylidenediphenol- epichlorohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • a curable composition comprising, consisting essentially of, or consisting of, (a) a resin comprising 4,4’-isopropylidenediphenol- epichlorohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the
  • the Figure shows the pot life (i.e., latency or gel time) at a temperature of 21 °C exhibited by the curable compositions set forth in the Example.
  • the invention provides a curable composition
  • a curable composition comprising, consisting essentially of, or consisting of, (a) a resin comprising 4,4’-isopropylidenediphenol-epichlorohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • inventive curable composition described herein comprising a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12: 1 to about 15: 1, provides a sufficient latency period (i.e., time to form a gel) to be manageable while inserting into a damaged pipe, has enough structural integrity to fill the pipe and maintain conformity, and efficiently cures at temperatures compatible with a hot water bladder or steam.
  • the inventive curable composition is (i) not too viscous prior to curing such that the composition is manageable and maneuverable, (ii) not too flowable (i.e., low viscosity) prior to curing such that the composition maintains structural integrity, and (iii) has the desirable ratio of resin to curing agent such that the composition has an ideal latency period and curing time and temperature.
  • the curable composition comprises a resin, wherein the resin comprises a 4,4’- isopropylidenediphenol-epichlorohydrin copolymer.
  • the term“4,4’- isopropylidenediphenol-epichlorohydrin copolymer” refers to a polymer derived from monomers 4,4’-isopropylidenediphenol (“bisphenol-A”) and epichlorohydrin.
  • “derived” when referring to a polymer means that the polymer has been synthesized from a formulation comprising said reagents or monomers. Accordingly, the polymer contains monomer units that are substantially the same structure of the monomer from which the monomer unit was made. For example, during the formation of a 4,4’- isopropylidenediphenol-epichlorohydrin copolymer, all or substantially all of the
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can have monomer units derived from monomers, 4,4’-isopropylidenediphenol and epichlorohydrin, in any suitable ratio.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can exist as an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer.
  • the 4, 4’ -isopropylidenedi phenol -epichlorohydrin copolymer is an alternating copolymer.
  • the monomer units derived from 4,4’-isopropylidenediphenol and epichlorohydrin can be present in a molar ratio of about 1 : 1.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can have any suitable molecular weight, e.g., weight average molecular weight, prior to curing.
  • the 4,4’- isopropylidenediphenol-epichlorohydrin copolymer can have a weight average molecular weight of about 10,000 Da or less, for example, about 8,000 Da or less, about 6,000 Da or less, about 5,000 Da or less, about 4,000 Da or less, about 2,000 Da or less, or about 1,000 Da or less.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can have a weight average molecular weight of about 400 Da or more, for example, about 500 Da or more, about 600 Da or more, about 700 Da or more, about 800 Da or more, or about 900 Da or more.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can have a weight average molecular weight bounded by any two of the aforementioned endpoints.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can have a weight average molecular weight of from about 400 Da to about 10,000 Da, from about 400 Da to about 8,000 Da, from about 400 Da to about 6,000 Da, from about 400 Da to about 5,000 Da, from about 400 Da to about 4,000 Da, from about 400 Da to about 2,000 Da, from about 400 Da to about 1,000 Da, from about 500 Da to about 10,000 Da, from about 600 Da to about 10,000 Da, from about 700 Da to about 10,000 Da, from about 800 Da to about 10,000 Da, from about 900 Da to about 10,000 Da, or from about 800 Da to about 5,000 Da.
  • the 4, 4’ -isopropylidenedi phenol -epichlorohydrin copolymer is of the formula:
  • n is an integer from 0 to about 20 (e.g., from 0 to about 10, from 0 to about 5, from 1 to about 20, from 1 to about 10, from 1 to about 5, from 2 to about 20, from 2 to about 10, or from 2 to about 5). In preferred embodiments, n is an integer from 0 to about 10.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer is EPONTM Resin 828, commercially available from Hexion Inc. (Columbus, OH).
  • the resin can comprise any suitable amount of 4,4’-isopropylidenediphenol- epichlorohydrin copolymer.
  • the resin can comprise about 80 wt.% or more of the 4,4’- isopropylidenediphenol-epichlorohydrin copolymer, for example, about 82 wt.% or more, about 84 wt.% or more, about 85 wt.% or more, about 86 wt.% or more, about 88 wt.% or more, about 90 wt.% or more, about 92 wt.% or more, about 94 wt.% or more, or about 95 wt.% or more.
  • the resin can comprise 100 wt.% or less of the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer, for example, 99.9 wt.% or less, 99.5 wt.% or less, about 99 wt.% or less, about 98 wt.% or less, about 97 wt.% or less, about 96 wt.% or less, or about 95 wt.% or less.
  • the resin can comprise the 4,4’- isopropylidenediphenol-epichlorohydrin copolymer in an amount bounded by any two of the aforementioned endpoints.
  • the resin can comprises from about 80 wt.% to 100 wt.% 4,4’-isopropylidenediphenol-epichlorohydrin copolymer, from about 82 wt.% to 100 wt.%, from about 84 wt.% to 100 wt.%, from about 85 wt.% to 100 wt.%, from about 86 wt.% to 100 wt.%, from about 88 wt.% to 100 wt.%, from about 90 wt.% to 100 wt.%, from about 92 wt.% to 100 wt.%, from about 94 wt.% to 100 wt.%, from about 95 wt.% to 100 wt.%, from about 80 wt.% to 99.9 wt.%, from about 80 wt.% to 99.5 wt.%, from about 80 wt.% to about 99 wt.%, from about 85 wt.%
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer can have any suitable intrinsic viscosity prior to curing.
  • the 4,4’- isopropylidenediphenol-epichlorohydrin copolymer has an intrinsic viscosity of from about 5,000 cps to about 20,000 cps (e.g., from about 5,000 cps to about 15,000 cps, from about 5,000 cps to about 12,000 cps, from about 10,000 cps to about 20,000 cps, from about 10,000 cps to about 15,000 cps, from about 10,000 cps to about 14,000 cps, from about 10,000 cps to about 12,000 cps, or from about 11,000 cps to about 12,000 cps) when stored at a temperature of 22 °C.
  • the 4,4’-isopropylidenediphenol-epichlorohydrin copolymer has an intrinsic viscosity of from about 11,000 cps to about 12,000 cps when stored at a temperature of 22 °C.
  • 4,4’-isopropylidenediphenol-epichlorohydrin copolymer is the only component of the resin.
  • the resin is free of any other component (i.e., other than 4,4’-isopropylidenediphenol-epichlorohydrin copolymer) that has a material effect on the curable composition (e.g., a diluent or a curing agent such as dicyandiamide).
  • the resin consists essentially of or consists of 4,4’- isopropylidenediphenol-epichlorohydrin copolymer.
  • the resin consists essentially of 4,4’-isopropylidenediphenol-epichlorohydrin copolymer
  • other components present in the resin can be the starting materials necessary for the formation of the 4,4’- isopropylidenediphenol-epichlorohydrin copolymer.
  • the resin consists of 4,4’- isopropylidenediphenol-epichlorohydrin copolymer
  • 4,4’-isopropylidenediphenol- epichlorohydrin copolymer is the only component of the resin.
  • the curable composition further comprises a diluent.
  • the diluent can be any substance used to modify the viscosity of the curable composition.
  • the diluent can be a monofunctional epoxide.
  • the monofunctional epoxide can be an epoxide of ethylene, propylene, butylene, styrene, cyclohexene, etc., and combinations thereof.
  • the diluent is a glycidyl ether of a
  • the diluent can be a glycidyl ether of any C 4 to Ci4 aliphatic or aromatic alcohols (e.g., phenol, cresols, /c/V-butyl phenol, butanol, or 2- ethylhexanol).
  • Ci4 aliphatic or aromatic alcohols e.g., phenol, cresols, /c/V-butyl phenol, butanol, or 2- ethylhexanol.
  • the diluent is a monofunctional glycidyl ether.
  • the term“monofunctional glycidyl ether” refers to a compound comprising an ether moiety, wherein the ether moiety has been formed between the primary alcohol substituent of glycidol and the hydroxyl group of an alkyl alcohol, aryl alcohol, arylalkyl alcohol, heteroaryl alcohol, or heteroalkyl alcohol.
  • the monofunctional glycidyl ether is a compound comprising an ether moiety, wherein the ether moiety has been formed between the primary alcohol substituent of glycidol and a straight or branched, saturated or unsaturated alkyl alcohol.
  • the monofunctional glycidyl ether is a compound comprising an ether moiety, wherein the ether moiety has been formed between the primary alcohol substituent of glycidol and C 12-C14 alkyl alcohol (“alkyl C12-C 14 glycidyl ether”).
  • the monofunctional glycidyl ether is of the formula
  • the monofunctional glycidyl ether can be EPODIL® 748, commercially available from Evonik Industries (Essen, North Rhine-Westphalia, Germany).
  • the curable composition can comprise any suitable amount of diluent (e.g., monofunctional glycidyl ether).
  • the curable composition can comprise 0.1 wt.% or more of the diluent, for example, 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 3 wt.% or more, about 4 wt.% or more, or about 5 wt.% or more.
  • the curable composition can comprise about 20 wt.% or less of the diluent, for example, about 18 wt.% or less, about 16 wt.% or less, about 15 wt.% or less, about 14 wt.% or less, about 12 wt.% or less, about 10 wt.% or less, about 8 wt.% or less, about 6 wt.% or less, or about 5 wt.% or less.
  • the curable composition can comprise the diluent in an amount bounded by any two of the aforementioned endpoints.
  • the curable composition can comprise up to about 20 wt.% diluent, up to about 18 wt.%, up to about 16 wt.%, up to about 15 wt.%, up to about 14 wt.%, up to about 12 wt.%, up to about 10 wt.%, up to about 8 wt.%, up to about 6 wt.%, up to about 5 wt.%, from 0.1 wt.% to about 20 wt.%, from 0.1 wt.% to about 10 wt.%, from 0.1 wt.% to about 5 wt.%, from 0.5 wt.% to about 20 wt.%, from about 1 wt.% to about 20 wt.%, from about 5 wt.% to about 15 wt.%, from 0.1 wt.% to about 10 wt.%, from about 0.5 wt.% to about 10 wt.%, from about 1 wt
  • the curable composition comprises from 0.1 wt.% to about 20 wt.% diluent. In certain embodiments, the curable composition comprises from about 1 wt.% to about 10 wt.% diluent.
  • the curable composition comprises one or more curing agents.
  • the term“curing agent” refers to any compound capable of reacting with the resin to produce a networked polymer comprising polyether groups.
  • the curable composition comprises the resin and the one or more curing agents wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1 (e.g., about 12: 1 to about 14: 1, about 12: 1 to about 13:1, about 13: 1 to about 15: 1, about 14: 1 to about 15 : 1, about 13 : 1 to about 14: 1, about 12: 1, about 13 : 1, about 14: 1, or about 15 : 1).
  • the weight percentage ratio of the resin to the one or more curing agents is from about 12: 1 to about 14: 1.
  • the weight percentage ratio of the resin to the one or more curing agents is about 12: 1.
  • the curing agent is a carboxylic acid salt of a tertiary amine.
  • at least one of the one or more curing agents is of Formula (I):
  • A is -0-, -CH2-, or -NR’-, R’ is hydrogen or an optionally substituted C1-C10 alkyl or C2-C10 alkenyl group;
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group can be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion.
  • C1-C10 alkyl group refers to a chemical substituent comprising from 1 to 10 (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms.
  • the C1-C10 alkyl group can be saturated, unsaturated when the alkyl group is C2-C10 (i.e., alkenyl), branched, straight-chained, cyclic when the alkyl group is C3-C10, or a combination thereof.
  • C1-C10 alkyl or C2-C10 alkenyl groups includes methyl, ethyl, «-propyl, iso propyl, «-butyl, sec-butyl, tert- butyl, «-pentyl, sec-pentyl, «eo-pentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, or 4- pentenyl.
  • the C1-C10 alkyl or C2-C10 alkenyl group is further substituted, e.g., with one or more alkyl substituents, aryl substituents, heteroatoms, e.g., O,
  • A is -O-, -CH2-, or -NH-.
  • R is a Ci-Ce alkylene chain, wherein the hydroxyl group can be present attached to any of the carbon atoms of the alkylene chain.
  • the phrase“C1-C6 alkylene chain” refers to a divalent alkyl chain (i.e., capable of connecting to two different atoms, for example, a nitrogen atom and an oxygen atom) containing from one to six carbon atoms.
  • the Ci-Ce alkylene chain can be saturated, branched, straight-chained, cyclic when the chain is C3-C6 alkylene, or a combination thereof.
  • the hydroxyl group can be attached to any of the carbon atoms of the C 1-C6 alkylene chain such that the hydroxyl group forms a primary alcohol, secondary alcohol, or tertiary alcohol. In certain embodiments, the hydroxyl group is attached to the C1-C6 alkylene chain such that the hydroxyl group forms a primary alcohol.
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl.
  • C1-C20 alkyl refers to a chemical substituent comprising from 1 to 20 (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) carbon atoms.
  • the C1-C20 alkyl group can be saturated, unsaturated (i.e., C2-C20 alkenyl), branched, straight- chained, cyclic when the alkyl group is C3-C20, or a combination thereof.
  • C1-C20 alkyl or C2-C20 alkenyl groups is methyl, ethyl, «-propyl, Ao-propyl, «-butyl, sec- butyl, /c/7-butyl, «-pentyl, sec-pentyl, «eo-pentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, or 4-pentenyl.
  • the C 1-C20 alkyl or C2-C20 alkenyl group is further substituted with one or more alkyl substituents, aryl substituents, heteroatoms, or combinations thereof.
  • the phrase“C1-C20 haloalkyl” refers to a C 1-C20 alkyl that has been substituted with one or more halogens (e.g., fluoro, chloro, bromo, iodo).
  • C 1-C20 haloalkyl or C2-C20 haloalkenyl is a perfluorinated substituent.
  • C6-C10 aryl refers to an aromatic chemical substituent comprising from 6 to 10 (i.e., 6, 7, 8, 9, or 10) carbon atoms.
  • one or more carbon atoms of the C6-C10 aryl group can be replaced with a nitrogen atom as long as the aromaticity of the C6-C10 aryl group is maintained.
  • An exemplary list of C6-C 10 aryl groups is phenyl, naphthyl, biphenyl, and pyridyl.
  • the C6-C10 aryl group is further substituted with one or more alkyl substituents, heteroatoms, or combinations thereof.
  • the terms“independent” and“independently,” when referring to one or more constituent means that each substituent is individually selected from the list and can be the same or different.
  • the tertiary amine component of the one or more curing agents is of Formula (I) and is selected from N-hydroxypropylpiperidine, N- hydroxyethylmorpholine, 2-methyl-N-hydroxyethylpiperidine,
  • X is the carboxylate anion of a carboxylic acid comprising from 1 to about 40 carbon atoms.
  • the carboxylate anion can be derived by replacing the acidic hydrogen of any carboxylic acid with a suitable cation.
  • the carboxylic acid comprises from 1 to about 40 carbon atoms, preferably 1 to about 24 carbon atoms.
  • An exemplary list of carboxylic acids is monocarboxylic acids such as tall oil fatty acid (TOFA), oleic acid, acetic acid, propanoic acid, 2-ethylhexanoic acid, decanoic acid, and hexanoic acid, and dimeric acids such as succinic acid, glutaric acid, adipic acid, or pimelic acid.
  • TOFA tall oil fatty acid
  • oleic acid acetic acid
  • propanoic acid 2-ethylhexanoic acid
  • decanoic acid decanoic acid
  • hexanoic acid and dimeric acids
  • the carboxylic acid is acetic acid, hexanoic acid, or tall oil fatty acid.
  • At least one of the one or more curing agents is of Formula (II):
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group can be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion.
  • X is the carboxylate anion of acetic acid, hexanoic acid, or tall oil fatty acid.
  • at least one of the one or more curing agents is of Formula (III):
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
  • X is the carboxylate anion of acetic acid, hexanoic acid, or tall oil fatty acid.
  • At least one of the one or more curing agents is
  • ANC AMINE® 2910 Curing Agent commercially available from Air Products (Allentown, PA).
  • at least one of the one or more curing agents is ANCAMINE® 2911 Curing Agent, commercially available from Air Products (Allentown, PA).
  • the one or more curing agents can have any suitable intrinsic viscosity prior to curing.
  • the one or more curing agents have an intrinsic viscosity of from about 1 cps to about 2,000 cps (e.g., from about 1 cps to about 1,000 cps, from about 1 cps to about 500 cps, from about 1 cps to about 200 cps, from about 10 cps to about 2,000 cps, from about 10 cps to about 1,000 cps, from about 10 cps to about 500 cps, from about 10 cps to about 200 cps, from about 30 cps to about 2,000 cps, from about 30 cps to about 1,000 cps, from about 30 cps to about 500 cps, from about 30 cps to about 200 cps, or from about 30 cps to about 60 cps) when stored at a temperature
  • the curable composition further comprises a latent curative such as dicyandi amide.
  • the curable composition can comprises any suitable amount of dicyandiamide.
  • the curable composition can comprise from about 0.1 wt.% to about 10 wt.% (e.g., from about 0.1 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 1 wt.%) of dieyamii amide in certain embodiments, the curable composition s substantially free of dicyandiamide.
  • curable compositions comprising the one or more curing agents contain less than about 0.1 wt.%, less than about 0.05 wt.%, and in some cases 0 wt.% of dicyandiamide.
  • the curable composition can comprise styrene containing compounds (e.g., styrene), in some embodiments, the curable composition is substantially free of styrene containing compounds.
  • substantially free refers to a curable composition that comprises less than about 0.5 wt.% styrene containing compounds (e.g., less than about 0.1 wt.%, less than about 0.05 wt.%, or less than about 0.01 wt.%). In certain embodiments, the curable composition does not contain a styrene containing compound.
  • the curable composition can comprise anhydride containing compounds
  • the curable composition is substantially free of anhydride containing compounds.
  • substantially free refers to a curable composition that comprises less than about 0.5 wt.% anhydride containing compounds (e.g., less than about 0.1 wt.%, less than about 0.05 wt.%, or less than about 0.01 wt.%).
  • the curable composition does not contain an anhydride containing compound.
  • the curable composition can have any suitable intrinsic viscosity prior to curing.
  • the curable composition has an intrinsic viscosity of from about 5,000 cps to about 20,000 cps (e.g., from about 5,000 cps to about 15,000 cps, from about 5,000 cps to about 12,000 cps, from about 8,000 cps to about 20,000 cps, from about 8,000 cps to about 15,000 cps, from about 8,000 cps to about 14,000 cps, from about 8,000 cps to about 12,000 cps, from about 8,000 cps to about 10,000 cps, or from about 9,000 cps to about 10,000 cps) when stored at a temperature of 22 °C.
  • the curable composition has an intrinsic viscosity of from about 9,000 cps to about 10,000 cps when stored at a temperature of 22 °C.
  • the curable composition further comprises one or more additives selected from pigments, dispersing agents, thixotropes, rheology modifiers, defoamers, fibers, accelerators, fillers, or any combination thereof.
  • the curable composition can comprise any suitable amount of the one or more additives so long as the ratio of the weight percentage of the resin to the weight percentage of the curing agent or curing agents is from about 12: 1 to about 15: 1.
  • the curable composition can comprise up to about 50 wt.% of the one or more additives, for example, up to about 40 wt.%, up to about 30 wt.%, up to about 20 wt.%, up to about 10 wt.%, or up to about 5 wt.%.
  • the curable composition consists essentially of or consists of the resin and the curing agent or curing agents (i.e., contains 0 wt.% of the one or more additives).
  • the curable composition can be cured at any suitable temperature.
  • the curable composition can be cured at a temperature of about 60 °C to about 85 °C (e.g., about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, or about 85 °C).
  • the curable composition can be cured at a temperature of about 60 °C to about 85 °C
  • the curable composition can be cured using a hot water bladder.
  • the curable composition requires a temperature of at least about 85 °C (e.g., at least about 85 °C, at least about 90 °C, at least about 95 °C, or at least about 100 °C).
  • the curable composition can be cured at a temperature of at least about 85 °C
  • the curable composition can be cured using steam.
  • a benefit of the curable composition described herein is the extended pot life (i.e., latency or gel time) at elevated temperatures.
  • extended pot life i.e., latency or gel time
  • the phrases“gel time” or“latency” refer to the length of time necessary for the curable composition, or a liner impregnated with the curable composition, to begin to“kick” or“cure”.
  • the start of the“kick” or“cure” can be determined by a sudden increase in temperature (e.g., an increase in temperature of at least about 10 °C) of the curable composition and/or the liner impregnated with the curable composition, or by a change in color of the liner impregnated with the curable composition (e.g., the liner turns brown).
  • a longer gel time provides the user more time to insert a cured-in-place liner containing a curable composition into a pipe.
  • the curable composition described herein has a gel time (i.e., time to gel) of about 12 hours to about 24 hours at a temperature of 21 °C (e.g., about 12 hours to about 20 hours, about 12 hours to about 16 hours, about 16 hours to about 24 hours, about 20 hours to about 24 hours, or about 16 to about 20 hours).
  • the composition has a gel time of about 14 hours to about 22 hours at a temperature of 21 °C.
  • the composition has a gel time of about 16 hours to about 20 hours at a temperature of 21 °C.
  • the invention also provides a method of curing a cured-in-place liner, wherein the method comprises: (i) placing the cured-in-place liner in a pipe and (ii) heating the cured-in- place liner, wherein the cured-in-place liner contains a curable composition comprising, consisting essentially of, or consisting of, (a) a resin comprising 4,4’-isopropylidenediphenol- epichlorohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • the method comprises placing the cured-in-place liner in a pipe.
  • the cured-in- place liner can be placed in the pipe by any suitable method.
  • the liner can be inserted or pulled to a point of repair from an access point upstream of the point of repair or downstream of the point of repair.
  • the cured-in-place liner is inserted or pulled from an access point upstream of the point of repair.
  • the cured-in-place liner can be made of any suitable material.
  • the cured-in-place liner can be made of felt, polyester, fiberglass, cloth, vinyl, nylon, or any other material suitable for impregnation with the curable composition, or any combination thereof.
  • the pipe can be any suitable pipe used for any suitable application.
  • the pipe can be used to transfer water, sewage, chemicals, or any combination thereof.
  • the pipe can be any suitable size.
  • the pipe can be from about 1 inch to about 20 feet in diameter, for example, from about 2 inches to about 20 feet, from about 2 inches to about 10 feet, from about 2 inches to about 5 feet, or from about 2 inches to about 1 foot. In preferred embodiments the pipe is from about 2 inches to about 10 feet in diameter.
  • the method can include heating the cured-in-place liner.
  • the cured-in-place liner can be heated to any suitable temperature.
  • the cured-in-place liner is heated to a temperature of from about 60 °C to about 85 °C (e.g., about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, or about 85 °C) to begin a curing process.
  • the cured-in-place liner is heated to a temperature of at least about 85 °C (e.g., at least about 85 °C, at least about 90 °C, at least about 95 °C, or at least about 100 °C) to begin a curing process.
  • a temperature of at least about 85 °C e.g., at least about 85 °C, at least about 90 °C, at least about 95 °C, or at least about 100 °C
  • a curable composition comprising, (a) a resin comprising 4,4’- isopropylidenediphenol-epichlorohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • A is -0-, -CH2-, or -NR’-, R’ is hydrogen or an optionally substituted C1-C10 alkyl or C2-C10 alkenyl group;
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group may be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion.
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group may be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion.
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and X is a carboxyl ate anion.
  • a curable composition comprising, (a) a resin comprising 4,4’- isopropylidenediphenol-epichlorohydrin copolymer and (b) one or more curing agents wherein at least one of the one or more curing agents is of Formula (II):
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group may be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12:1 to about 15: 1.
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
  • a method of curing a cured-in-place liner comprising: (i) placing the cured-in-place liner in a pipe and (ii) heating the cured-in-place liner, wherein the cured-in-place liner contains a curable composition comprising, (a) a resin comprising 4,4’- isopropylidenediphenol-epichlorohydrin copolymer and (b) one or more curing agents, wherein a ratio of a weight percentage of the resin to a weight percentage of the curing agent or curing agents is from about 12: 1 to about 15: 1.
  • A is -0-, -CH2-, or -NR’-, R’ is hydrogen or an optionally substituted C1-C10 alkyl or C2-C10 alkenyl group;
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group may be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C2 0 alkyl, C2-C2 0 alkenyl, C1-C2 0 haloalkyl, C2-C2 0 haloalkenyl, or C 6 -C1 0 aryl; and
  • X is a carboxylate anion.
  • R is a C1-C6 alkylene chain, wherein the hydroxyl group may be attached to any of the carbon atoms of the alkylene chain;
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and
  • X is a carboxylate anion.
  • Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
  • This example demonstrates the effect of ratio of wt.% of resin to curing agent on pot life, exhibited by a curable composition at 21 °C, as measured by the gel time of the curable composition.
  • Curable Compositions 1-6 as set forth in Table 1 below were prepared using the ratios of resin (EPONTM Resin 828) to curing agent (ANCAMINE® 2910 Curing Agent).
  • the resulting mixtures were put in a liner and placed at a temperature of 21 °C until a sudden change in temperature (i.e., a temperature change of at least 10 °C) of the curable
  • the pot life at 21 °C is linearly correlated with the ratio of wt.% of resin to curing agent.
  • Comparative Curable Compositions 1 and 2 had too low of a viscosity to be useful for cured- in-place pipe applications.
  • Comparative Curable Compositions 5 and 6 had too high of a viscosity to be useful for cured-in-place pipe applications.
  • Comparative Curable Compositions 5 and 6 were too viscous to be efficiently pumped into a liner, making production difficult and their use in cured-in-place pipe applications unlikely.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition durcissable présentant un temps de durcissement amélioré à des températures ambiantes, la composition durcissable comprenant (a) une résine, par exemple, un copolymère de 4,4'-isopropylidènediphénol-épichlorhydrine et (b) un ou plusieurs agents de durcissement, un rapport d'un pourcentage en poids de la résine à un pourcentage en poids de l'agent de durcissement ou des agents de durcissement étant d'environ 12:1 à environ 15:1. L'invention concerne également un procédé de durcissement d'un revêtement durci en place, le revêtement durci en place contenant la composition durcissable ci-dessus.
PCT/US2018/050008 2018-09-07 2018-09-07 Composition durcissable pour tuyaux durcis en place Ceased WO2020050858A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA3111761A CA3111761A1 (fr) 2018-09-07 2018-09-07 Composition durcissable pour tuyaux durcis en place
JP2021512921A JP7281222B2 (ja) 2018-09-07 2018-09-07 現場硬化パイプ用硬化性組成物
PCT/US2018/050008 WO2020050858A1 (fr) 2018-09-07 2018-09-07 Composition durcissable pour tuyaux durcis en place
AU2018440151A AU2018440151B2 (en) 2018-09-07 2018-09-07 Curable composition for cured in place pipes
EP18789272.4A EP3847204A1 (fr) 2018-09-07 2018-09-07 Composition durcissable pour tuyaux durcis en place
MX2021002470A MX2021002470A (es) 2018-09-07 2018-09-07 Composicion curable para tuberias curadas en su lugar.
JP2023076640A JP2023113624A (ja) 2018-09-07 2023-05-08 現場硬化パイプ用硬化性組成物
AU2024204145A AU2024204145A1 (en) 2018-09-07 2024-06-18 Curable composition for cured in place pipes

Applications Claiming Priority (1)

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PCT/US2018/050008 WO2020050858A1 (fr) 2018-09-07 2018-09-07 Composition durcissable pour tuyaux durcis en place

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JP (2) JP7281222B2 (fr)
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US10865305B2 (en) 2018-09-07 2020-12-15 Pipefusion Cipp Corporation Method of curing a cured-in-place liner

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US20070116961A1 (en) * 2005-11-23 2007-05-24 3M Innovative Properties Company Anisotropic conductive adhesive compositions
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US20180171067A1 (en) * 2016-12-21 2018-06-21 Evonik Degussa Gmbh N-hydroxyl ethyl piperidine (nhep): a novel curing agent for epoxy systems

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US20100227981A1 (en) 2009-03-04 2010-09-09 Air Products And Chemicals, Inc. Epoxide-based composition
EP2981565B1 (fr) 2013-04-05 2017-10-04 Evonik Degussa GmbH Agents de durcissement époxy mono-composants comprenant des hydroxyalkylaminocycloalcanes

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US3792016A (en) * 1972-01-06 1974-02-12 Minnesota Mining & Mfg Metal imidazolate-catalyzed systems
US20070116961A1 (en) * 2005-11-23 2007-05-24 3M Innovative Properties Company Anisotropic conductive adhesive compositions
US20100184925A1 (en) * 2007-06-13 2010-07-22 Basf Se Catalyst for curing epoxides
US20140243456A1 (en) * 2013-02-28 2014-08-28 Air Products And Chemicals, Inc. Anhydride Accelerators for Epoxy Resin Systems
US20140303342A1 (en) * 2013-02-28 2014-10-09 Air Products And Chemicals, Inc. One Component Epoxy Curing Agents Comprising Hydroxyalkylamino Cycloalkanes
US20180171067A1 (en) * 2016-12-21 2018-06-21 Evonik Degussa Gmbh N-hydroxyl ethyl piperidine (nhep): a novel curing agent for epoxy systems

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Publication number Priority date Publication date Assignee Title
US10865305B2 (en) 2018-09-07 2020-12-15 Pipefusion Cipp Corporation Method of curing a cured-in-place liner
US11130858B2 (en) 2018-09-07 2021-09-28 Pipefusion Cipp Corporation Curable compositions for cured-in-place pipes

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JP2022503662A (ja) 2022-01-12
MX2021002470A (es) 2021-04-29
EP3847204A1 (fr) 2021-07-14
AU2024204145A1 (en) 2024-07-04
CA3111761A1 (fr) 2020-03-12
JP2023113624A (ja) 2023-08-16
JP7281222B2 (ja) 2023-05-25
AU2018440151A1 (en) 2021-03-25

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