CA3111761A1 - Curable composition for cured in place pipes - Google Patents
Curable composition for cured in place pipes Download PDFInfo
- Publication number
- CA3111761A1 CA3111761A1 CA3111761A CA3111761A CA3111761A1 CA 3111761 A1 CA3111761 A1 CA 3111761A1 CA 3111761 A CA3111761 A CA 3111761A CA 3111761 A CA3111761 A CA 3111761A CA 3111761 A1 CA3111761 A1 CA 3111761A1
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- Canada
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 143
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- -1 e.g. Polymers 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 105
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 125000002947 alkylene group Chemical group 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 125000003342 alkenyl group Chemical group 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 17
- 125000001188 haloalkyl group Chemical group 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims 2
- 239000003085 diluting agent Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 6
- 125000001033 ether group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000002118 epoxides Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 150000003138 primary alcohols Chemical group 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000003784 tall oil Substances 0.000 description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000006024 2-pentenyl group Chemical group 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IHPYMWDTONKSCO-UHFFFAOYSA-N 2,2'-piperazine-1,4-diylbisethanesulfonic acid Chemical compound OS(=O)(=O)CCN1CCN(CCS(O)(=O)=O)CC1 IHPYMWDTONKSCO-UHFFFAOYSA-N 0.000 description 1
- DUAIISPCCJPFDG-UHFFFAOYSA-N 2-(2-methylpiperidin-1-yl)ethanol Chemical compound CC1CCCCN1CCO DUAIISPCCJPFDG-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 description 1
- VARKIGWTYBUWNT-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanol Chemical compound OCCN1CCN(CCO)CC1 VARKIGWTYBUWNT-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- PLRXAFVBCHEMGD-UHFFFAOYSA-N 3-piperidin-1-ylpropan-1-ol Chemical compound OCCCN1CCCCC1 PLRXAFVBCHEMGD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000007990 PIPES buffer Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001734 carboxylic acid salts Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- RJUAEBLXGFKZMS-UHFFFAOYSA-N piperidin-1-ylmethanol Chemical compound OCN1CCCCC1 RJUAEBLXGFKZMS-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
Landscapes
- 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
Disclosed is a curable composition with enhanced curing time at ambient temperatures, the curable composition including (a) a resin, e.g., 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. Also disclosed is a method of curing a cured-in-place liner, wherein the cured-in-place liner contains the above curable composition.
Description
CURABLE COMPOSITION FOR CURED IN PLACE PIPES
BACKGROUND OF THE INVENTION
[0001] 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.
BACKGROUND OF THE INVENTION
[0001] 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.
[0002] 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. Conventional methods for providing a curable composition with desirable qualities (i), (ii), and (iii), 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.
[0003] Existing curable compositions provide inadequate results for one or more of the desirable qualities (i), (ii), and (iii). In addition, economic production is also needed. For example, 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.
[0004] Thus, there remains an unmet need in the art for improved curable compositions that (i) have a sufficient latency period (i.e., time to form a gel) to permit inserting into a damaged pipe, (ii) have sufficient structural integrity to fill the pipe and maintain conformity, and/or (iii) efficiently cure at temperatures compatible with a hot water bladder or steam.
BRIEF SUMMARY OF THE INVENTION
BRIEF SUMMARY OF THE INVENTION
[0005] The invention provides 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.
[0006] The invention further provides 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):
R1 _____________________________________ R2 H X e OH
(II) wherein R is a Cl-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio 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.
R1 _____________________________________ R2 H X e OH
(II) wherein R is a Cl-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio 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.
[0007] 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.
8 PCT/US2018/050008 BRIEF DESCRIPTION OF THE DRAWINGS
[0008] 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.
DETAILED DESCRIPTION OF THE INVENTION
[0008] 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.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The invention provides 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.
[0010] The 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. In other words, 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.
[0011] The curable composition comprises a resin, wherein the resin comprises a 4,4'-isopropylidenediphenol-epichlorohydrin copolymer. As used herein, the term "4,4'-isopropylidenediphenol-epichlorohydrin copolymer" refers to a polymer derived from monomers 4,4'-isopropylidenediphenol ("bisphenol-A") and epichlorohydrin. As used herein, "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 epichlorohydrin is transformed such that it no longer has the chlorine atom and/or the epoxide group.
[0012] 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.
Typically, the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is an alternating copolymer. In an embodiment, the monomer units derived from 4,4'-isopropylidenediphenol and epichlorohydrin can be present in a molar ratio of about 1:1.
Typically, the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is an alternating copolymer. In an embodiment, the monomer units derived from 4,4'-isopropylidenediphenol and epichlorohydrin can be present in a molar ratio of about 1:1.
[0013] 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. Alternatively, or in addition, 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. Thus, the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer can have a weight average molecular weight bounded by any two of the aforementioned endpoints. For example, 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.
[0014] In an embodiment, the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is of the formula:
OH
_ n wherein 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. In some embodiments, the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is EPONTm Resin 828, commercially available from Hexion Inc. (Columbus, OH).
OH
_ n wherein 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. In some embodiments, the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is EPONTm Resin 828, commercially available from Hexion Inc. (Columbus, OH).
[0015] 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. Alternatively, or in addition, 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. Thus, the resin can comprise the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer in an amount bounded by any two of the aforementioned endpoints. For example, 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.% to about 95 wt.%, from about 90 wt.%
to about 99.9 wt.%, from about 90 wt.% to about 99.5 wt.%, from about 90 wt.% to about 99 wt.%, from about 90 wt.% to about 95 wt.%, or from about 95 wt.% to 99.9 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. Alternatively, or in addition, 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. Thus, the resin can comprise the 4,4'-isopropylidenediphenol-epichlorohydrin copolymer in an amount bounded by any two of the aforementioned endpoints. For example, 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.% to about 95 wt.%, from about 90 wt.%
to about 99.9 wt.%, from about 90 wt.% to about 99.5 wt.%, from about 90 wt.% to about 99 wt.%, from about 90 wt.% to about 95 wt.%, or from about 95 wt.% to 99.9 wt.%.
[0016] The 4,4'-isopropylidenediphenol-epichlorohydrin copolymer can have any suitable intrinsic viscosity prior to curing. In some embodiments, 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. In preferred embodiments, 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.
[0017] In preferred embodiments, 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is the only component of the resin. In such embodiments, 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). In certain embodiments, the resin consists essentially of or consists of 4,4'-isopropylidenediphenol-epichlorohydrin copolymer. When 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. When the resin consists of 4,4'-isopropylidenediphenol-epichlorohydrin copolymer, 4,4'-isopropylidenediphenol-epichlorohydrin copolymer is the only component of the resin.
[0018] In some embodiments, the curable composition further comprises a diluent. The diluent can be any substance used to modify the viscosity of the curable composition. For example, the diluent can be a monofunctional epoxide. For example, the monofunctional epoxide can be an epoxide of ethylene, propylene, butylene, styrene, cyclohexene, etc., and combinations thereof. In some embodiments, the diluent is a glycidyl ether of a monofunctional epoxide. For example, the diluent can be a glycidyl ether of any C4 to C14 aliphatic or aromatic alcohols (e.g., phenol, cresols, tert-butylphenol, butanol, or 2-ethylhexanol).
[0019] In certain embodiments, the diluent is a monofunctional glycidyl ether. As used herein, the term "monofunctional glycidyl ether" refers to a compound comprising an ether moiety, wherein the ether moiety has been formed between the primary alcohol sub stituent of glycidol and the hydroxyl group of an alkyl alcohol, aryl alcohol, arylalkyl alcohol, heteroaryl alcohol, or heteroalkyl alcohol. In certain embodiments, 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. In preferred embodiments, 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 C12-C14 alkyl alcohol ("alkyl C12-C14 glycidyl ether"). In some embodiments, the monofunctional glycidyl ether is of the formula C) C) 0, or combinations thereof. For example, the monofunctional glycidyl ether can be EPODIL
748, commercially available from Evonik Industries (Essen, North Rhine-Westphalia, Germany).
748, commercially available from Evonik Industries (Essen, North Rhine-Westphalia, Germany).
[0020] 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.
Alternatively, or in addition, 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. Thus, the curable composition can comprise the diluent in an amount bounded by any two of the aforementioned endpoints. For example, 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.%
to about wt.%, from about 5 wt.% to about 10 wt.%, from about 0.1 wt.% to about 5 wt.%, or from about 1 wt.% to about 5 wt.%. In some embodiments, 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.
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.
Alternatively, or in addition, 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. Thus, the curable composition can comprise the diluent in an amount bounded by any two of the aforementioned endpoints. For example, 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.%
to about wt.%, from about 5 wt.% to about 10 wt.%, from about 0.1 wt.% to about 5 wt.%, or from about 1 wt.% to about 5 wt.%. In some embodiments, 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.
[0021] The curable composition comprises one or more curing agents. As used herein, the term "curing agent" refers to any compound capable of reacting with the resin to produce a networked polymer comprising polyether groups. Generally, 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). In certain embodiments, the weight percentage ratio of the resin to the one or more curing agents is from about 12:1 to about 14:1. In preferred embodiments, the weight percentage ratio of the resin to the one or more curing agents is about 12:1.
[0022]
Typically, the curing agent is a carboxylic acid salt of a tertiary amine. In some embodiments, at least one of the one or more curing agents is of Formula (I):
(A) R1 _____________________________________ R2 N 0 xe OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-Cio alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
Typically, the curing agent is a carboxylic acid salt of a tertiary amine. In some embodiments, at least one of the one or more curing agents is of Formula (I):
(A) R1 _____________________________________ R2 N 0 xe OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-Cio alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0023] As used herein, the phrase "Ci-Cio 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 Ci-Cio alkyl group can be saturated, unsaturated when the alkyl group is C2-Cio (i.e., alkenyl), branched, straight-chained, cyclic when the alkyl group is C3-Cio, or a combination thereof An exemplary list of Ci-Cio alkyl or C2-Cio alkenyl groups includes methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, or 4-pentenyl. In certain embodiments, the Ci-Cio alkyl or C2-Cio alkenyl group is further substituted, e.g., with one or more alkyl substituents, aryl substituents, heteroatoms, e.g., 0, S, or N, or any combinations thereof. In certain embodiments, A is ¨0¨, ¨CH2¨, or ¨NH¨.
The Ci-Cio alkyl group can be saturated, unsaturated when the alkyl group is C2-Cio (i.e., alkenyl), branched, straight-chained, cyclic when the alkyl group is C3-Cio, or a combination thereof An exemplary list of Ci-Cio alkyl or C2-Cio alkenyl groups includes methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, or 4-pentenyl. In certain embodiments, the Ci-Cio alkyl or C2-Cio alkenyl group is further substituted, e.g., with one or more alkyl substituents, aryl substituents, heteroatoms, e.g., 0, S, or N, or any combinations thereof. In certain embodiments, A is ¨0¨, ¨CH2¨, or ¨NH¨.
[0024] As used herein, the term "substituted" means that one or more hydrogens on the designated atom or group are replaced with another group provided that the designated atom's normal valence is not exceeded. For example, when the substituent is oxo (i.e., =0), then two hydrogens on the carbon atom are replaced. Combinations of substituents are permissible provided that the substitutions do not significantly adversely affect synthesis or use of the curing agent.
[0025] R is a Ci-C6 alkylene chain, wherein the hydroxyl group can be present attached to any of the carbon atoms of the alkylene chain. As used herein, the phrase "Ci-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-C6 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 Ci-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 Ci-C6 alkylene chain such that the hydroxyl group forms a primary alcohol.
[0026] Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl. As used herein, the phrase "Ci-C2o 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 Ci-C2o 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 An exemplary list of Ci-C2o alkyl or C2-C2o alkenyl groups is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, or 4-pentenyl. In certain embodiments, the Ci-C2o alkyl or C2-C2o alkenyl group is further substituted with one or more alkyl substituents, aryl substituents, heteroatoms, or combinations thereof As used herein, the phrase "Ci-C2o haloalkyl" refers to a Ci-C2o alkyl that has been substituted with one or more halogens (e.g., fluor , chloro, bromo, iodo). In certain embodiments, Ci-C2o haloalkyl or C2-C2o haloalkenyl is a perfluorinated substituent. As used herein, the phrase "C6-Cio aryl" refers to an aromatic chemical substituent comprising from 6 to 10 (i.e., 6, 7, 8, 9, or 10) carbon atoms. In some embodiments, one or more carbon atoms of the C6-Cio aryl group can be replaced with a nitrogen atom as long as the aromaticity of the C6-Cio aryl group is maintained. An exemplary list of C6-Cio aryl groups is phenyl, naphthyl, biphenyl, and pyridyl. In certain embodiments, the C6-Cio aryl group is further substituted with one or more alkyl substituents, heteroatoms, or combinations thereof.
[0027] As used herein, the terms "independent" and "independently," when referring to one or more constituent (e.g., Ri and/or R2), means that each sub stituent is individually selected from the list and can be the same or different.
[0028] In certain embodiments, 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, 1,4-bis(2-hydroxyethyl)piperazine, N-hydroxymethylpiperidine, N-hydroxyethylpiperidine, and combinations thereof.
[0029] 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. In embodiments, 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. In certain embodiments, the carboxylic acid is acetic acid, hexanoic acid, or tall oil fatty acid.
[0030] In certain embodiments, at least one of the one or more curing agents is of Formula (II):
R1 _____________________________________ R2 H NI X e OH
(II) wherein R is a Cl-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion. In preferred embodiments of the one or more curing agents of Formula (II), X is the carboxylate anion of acetic acid, hexanoic acid, or tall oil fatty acid.
R1 _____________________________________ R2 H NI X e OH
(II) wherein R is a Cl-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion. In preferred embodiments of the one or more curing agents of Formula (II), X is the carboxylate anion of acetic acid, hexanoic acid, or tall oil fatty acid.
[0031] In preferred embodiments, at least one of the one or more curing agents is of Formula (III):
R1 _____________________________________ R2 N xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C20 alkenyl, Ci-C20 haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion. In preferred embodiments of the one or more curing agents of Formula (III), X is the carboxylate anion of acetic acid, hexanoic acid, or tall oil fatty acid.
R1 _____________________________________ R2 N xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C20 alkenyl, Ci-C20 haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion. In preferred embodiments of the one or more curing agents of Formula (III), X is the carboxylate anion of acetic acid, hexanoic acid, or tall oil fatty acid.
[0032] In some embodiments, at least one of the one or more curing agents is ANCAMINE 2910 Curing Agent, commercially available from Air Products (Allentown, PA). In certain embodiments, at least one of the one or more curing agents is ANCAMINE
2911 Curing Agent, commercially available from Air Products (Allentown, PA).
2911 Curing Agent, commercially available from Air Products (Allentown, PA).
[0033] The one or more curing agents can have any suitable intrinsic viscosity prior to curing. In some embodiments, 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 of 22 C. In preferred embodiments, the one or more curing agents have an intrinsic viscosity of from about 30 cps to about 60 cps when stored at a temperature of 22 C.
[0034] In some embodiments, the curable composition further comprises a latent curative such as dicyandiamide. The curable composition can comprises any suitable amount of dicyandiamide. For example, the curable composition can comprise from about 01. 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 dicyandiamide, in certain embodiments, die curable composition is substantially free of dicyandiamide. By "substantially free" it is meant that the 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.
[0035] While the curable composition can comprise styrene containing compounds (e.g., styrene), in some embodiments, the curable composition is substantially free of styrene containing compounds. As used herein, "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.
[0036] While the curable composition can comprise anhydride containing compounds, in some embodiments, the curable composition is substantially free of anhydride containing compounds. As used herein, "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.%). In certain embodiments, the curable composition does not contain an anhydride containing compound.
[0037] The curable composition can have any suitable intrinsic viscosity prior to curing.
In some embodiments, 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. In preferred embodiments, 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.
In some embodiments, 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. In preferred embodiments, 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.
[0038] In some embodiments, 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. Accordingly, 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.%. In certain embodiments, 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).
[0039] The curable composition can be cured at any suitable temperature.
For example, 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). In embodiments where 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.
In other embodiments, 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). In embodiments where the curable composition can be cured at a temperature of at least about 85 C, the curable composition can be cured using steam.
For example, 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). In embodiments where 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.
In other embodiments, 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). In embodiments where the curable composition can be cured at a temperature of at least about 85 C, the curable composition can be cured using steam.
[0040] In accordance with an embodiment of the invention, a benefit of the curable composition described herein is the extended pot life (i.e., latency or gel time) at elevated temperatures. As used herein, 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". For example, 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. Typically, 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). In some embodiments, the composition has a gel time of about 14 hours to about 22 hours at a temperature of 21 C. In certain embodiments, the composition has a gel time of about 16 hours to about 20 hours at a temperature of 21 C.
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. Typically, 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). In some embodiments, the composition has a gel time of about 14 hours to about 22 hours at a temperature of 21 C. In certain embodiments, the composition has a gel time of about 16 hours to about 20 hours at a temperature of 21 C.
[0041] 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.
[0042] 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. For example, 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. In preferred embodiments, the cured-in-place liner is inserted or pulled from an access point upstream of the point of repair.
[0043] The cured-in-place liner can be made of any suitable material. For example, 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.
[0044] The pipe can be any suitable pipe used for any suitable application.
For example, the pipe can be used to transfer water, sewage, chemicals, or any combination thereof. The pipe can be any suitable size. For example, 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 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.
For example, the pipe can be used to transfer water, sewage, chemicals, or any combination thereof. The pipe can be any suitable size. For example, 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 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.
[0045] The method can include heating the cured-in-place liner. The cured-in-place liner can be heated to any suitable temperature. In some embodiments, 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. In other embodiments, 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.
[0046] The invention is further illustrated by the following embodiments.
[0047] (1) 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.
[0048] (2) The curable composition of embodiment (1), wherein at least one of the one or more curing agents is of Formula (I):
2A) R1 _____________________________________ R2 N
OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-Cio alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
2A) R1 _____________________________________ R2 N
OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-Cio alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0049] (3) The curable composition of embodiment (1) or (2), wherein at least one of the one or more curing agents is of Formula (II):
R1 _____________________________________ R2 N 0 xe OH
(II) wherein R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 N 0 xe OH
(II) wherein R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0050] (4) The curable composition of any one of embodiments (1)-(3), wherein at least one of the one or more curing agents is of Formula (III):
R1 _____________________________________ R2 xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C20 alkyl, C2-C20 alkenyl, Ci-C20 haloalkyl, C2-C20 haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C20 alkyl, C2-C20 alkenyl, Ci-C20 haloalkyl, C2-C20 haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0051] (5) The curable composition of any one of embodiments (2)-(4), wherein X is the carboxylate anion of a carboxylic acid comprising from 1 to about 40 carbon atoms.
[0052] (6) The curable composition of any one of embodiments (1)-(5), wherein 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 14:1.
[0053] (7) The curable composition of embodiment (6), wherein the ratio of the weight percentage of the resin to the weight percentage of the curing agent or curing agents is about 12:1.
[0054] (8) The curable composition of any one of embodiments (1)-(7), wherein the composition requires a temperature of at least about 85 C to begin a curing process.
[0055] (9) The curable composition of any one of embodiments (1)-(7), wherein the composition begins a curing process at a temperature of about 60 C to about 85 C.
[0056] (10) The curable composition of any one of embodiments (1)-(9), wherein the composition has a gel time of about 12 hours to about 24 hours at a temperature of 21 C.
[0057] (11) The curable composition of embodiment (10), wherein the composition has a gel time of about 14 hours to about 22 hours at a temperature of 21 C.
[0058] (12) The curable composition of embodiment (11), wherein the composition has a gel time of about 16 hours to about 20 hours at a temperature of 21 C.
[0059] (13) 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):
R1 _____________________________________ R2 OH
(II) wherein R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio 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.
R1 _____________________________________ R2 OH
(II) wherein R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio 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.
[0060] (14) The curable composition of embodiment (13), wherein at least one of the one or more curing agents is of Formula (III):
R1 _____________________________________ R2 xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0061] (15) The curable composition of embodiment (13) or (14), wherein Xis the carboxylate anion of a carboxylic acid comprising from 1 to about 40 carbon atoms.
[0062] (16) The curable composition of any one of embodiments (13)-(15), wherein 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 14:1.
[0063] (17) The curable composition of embodiment (16), wherein the ratio of the weight percentage of the resin to the weight percentage of the curing agent or curing agents is about 12:1.
[0064] (18) The curable composition of any one of embodiments (13)-(17), wherein the composition requires a temperature of at least about 85 C to begin a curing process.
[0065] (19) The curable composition of any one of embodiments (13)-(17), wherein the composition begins a curing process at a temperature of about 60 C to about 85 C.
[0066] (20) The curable composition of any one of embodiments (13)-(19), wherein the composition has a gel time of about 12 hours to about 24 hours at a temperature of 21 C.
[0067] (21) The curable composition of embodiment (20), wherein the composition has a gel time of about 14 hours to about 22 hours at a temperature of 21 C.
[0068] (22) The curable composition of embodiment (21), wherein the composition has a gel time of about 16 hours to about 20 hours at a temperature of 21 C.
[0069] (23) 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, (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.
[0070] (24) The method of embodiment (23), wherein at least one of the one or more curing agents is of Formula (I):
(A) R1 _____________________________________ R2 HI\11 Xe OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-Cio alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
(A) R1 _____________________________________ R2 HI\11 Xe OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-Cio alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0071] (25) The method of embodiment (23) or (24), wherein at least one of the one or more curing agents is of Formula (II):
R1 _____________________________________ R2 H/NI Xe OH
(II) wherein R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 H/NI Xe OH
(II) wherein R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0072] (26) The method of any one of embodiments (23)-(25), wherein at least one of the one or more curing agents is of Formula (III):
R1 _____________________________________ R2 xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 xe OH
(III) wherein Ri and R2 are each independently hydrogen, hydroxyl, or an optionally substituted Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
[0073] (27) The method of any one of embodiments (23)-(26), wherein 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 14:1.
[0074] (28) The method of embodiment (27), wherein the ratio of the weight percentage of the resin to the weight percentage of the curing agent or curing agents is about 12:1.
[0075] (29) The method of any one of embodiments (23)-(28), wherein the cured-in-place liner is heated to a temperature of at least about 85 C.
[0076] (30) The method of any one of embodiments (23)-(28), wherein the cured-in-place liner is heated to a temperature of about 60 C to about 85 C.
EXAMPLE
EXAMPLE
[0077] The following example further illustrates the invention but, of course, should not be construed as in any way limiting its scope.
[0078] 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.
[0079] 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 compositions was observed. The pot life (i.e., time to gel) results are set forth in Table 1 and are plotted in the Figure.
Table 1: Curable Composition vs. Pot Life at 21 C
Curable Ratio of wt.% of Resin to Pot Life at 21 C (hours) Composition Curing Agent 1 (Comparative) 10:1 9 2 (Comparative) 11:1 12 3 (Inventive) 12:1 18 4 (Inventive) 15:1 22 5 (Comparative) 18:1 30 6 (Comparative) 20:1 38
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 compositions was observed. The pot life (i.e., time to gel) results are set forth in Table 1 and are plotted in the Figure.
Table 1: Curable Composition vs. Pot Life at 21 C
Curable Ratio of wt.% of Resin to Pot Life at 21 C (hours) Composition Curing Agent 1 (Comparative) 10:1 9 2 (Comparative) 11:1 12 3 (Inventive) 12:1 18 4 (Inventive) 15:1 22 5 (Comparative) 18:1 30 6 (Comparative) 20:1 38
[0080] As is apparent from the results set forth in Table 1 and the Figure, the pot life at 21 C is linearly correlated with the ratio of wt.% of resin to curing agent.
However, Comparative Curable Compositions 1 and 2 had too low of a viscosity to be useful for cured-in-place pipe applications. For example, when fitting a pipe with a liner containing comparative Curable Compositions 1 and 2, the curable composition drained to the bottom hemisphere of the pipe, resulting in inadequate fittings. Comparative Curable Compositions and 6 had too high of a viscosity to be useful for cured-in-place pipe applications. For example, 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.
However, Comparative Curable Compositions 1 and 2 had too low of a viscosity to be useful for cured-in-place pipe applications. For example, when fitting a pipe with a liner containing comparative Curable Compositions 1 and 2, the curable composition drained to the bottom hemisphere of the pipe, resulting in inadequate fittings. Comparative Curable Compositions and 6 had too high of a viscosity to be useful for cured-in-place pipe applications. For example, 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.
[0081] Curable Compositions 3 and 4 with ratios of wt.% of resin to curing agent of 12:1 and 15:1, respectively, provided adequate pot life times (i.e., 18 hours and 22 hours, respectively) and have a viscosity suitable for filling a liner, while maintaining structure for cured-in-place pipe applications.
[0082] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
[0083] The use of the terms "a" and "an" and "the" and "at least one" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term "at least one"
followed by a list of one or more items (for example, "at least one of A and B") is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing"
are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
followed by a list of one or more items (for example, "at least one of A and B") is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing"
are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
[0084] The terms "about" and "around," as used herein to modify a numerical value, indicate a close range surrounding the numerical value. Thus, if "X" is the value, "about X"
or "around X" indicates a value of from 0.9X to 1.1X, e.g., from 0.95X to 1.05X or from 0.99X to 1.01X. A reference to "about X" or "around X" specifically indicates at least the values X, 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, 1.01X, 1.02X, 1.03X, 1.04X, and 1.05X.
Accordingly, "about X" and "around X" are intended to teach and provide written description support for a claim limitation of, e.g., "0.98X."
or "around X" indicates a value of from 0.9X to 1.1X, e.g., from 0.95X to 1.05X or from 0.99X to 1.01X. A reference to "about X" or "around X" specifically indicates at least the values X, 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, 1.01X, 1.02X, 1.03X, 1.04X, and 1.05X.
Accordingly, "about X" and "around X" are intended to teach and provide written description support for a claim limitation of, e.g., "0.98X."
[0085] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Claims (20)
1. 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.
2. The curable composition of claim 1, wherein at least one of the one or more curing agents is of Formula (I):
(A) R1 _____________________________________ R2 N,c) xe H
OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Clo 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-C2o alkyl, C2-C20 alkenyl, C1-C2o haloalkyl, C2-C2o haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
(A) R1 _____________________________________ R2 N,c) xe H
OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Clo 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-C2o alkyl, C2-C20 alkenyl, C1-C2o haloalkyl, C2-C2o haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
3. The curable composition of claim 1 or 2, wherein at least one of the one or more curing agents is of Formula (II):
R1 _____________________________________ R2 Xe OH
(II) wherein 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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 Xe OH
(II) wherein 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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
4. The curable composition of any one of claims 1-3, wherein at least one of the one or more curing agents is of Formula (III):
R1 _____________________________________ R2 xe OH
(III) wherein 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.
R1 _____________________________________ R2 xe OH
(III) wherein 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.
5. The curable composition of any one of claims 2-4, wherein X is the carboxylate anion of a carboxylic acid comprising from 1 to about 40 carbon atoms.
6. The curable composition of any one of claims 1-5, wherein 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 14:1.
7. The curable composition of any one of claims 1-6, wherein the ratio of the weight percentage of the resin to the weight percentage of the curing agent or curing agents is about 12:1.
8. The curable composition of any one of claims 1-7, wherein the composition requires a temperature of at least about 85 C to begin a curing process.
9. The curable composition of any one of claims 1-7, wherein the composition begins a curing process at a temperature of about 60 C to about 85 C.
10. The curable composition of any one of claims 1-9, wherein the composition has a gel time of about 12 hours to about 24 hours at a temperature of 21 C.
11. The curable composition of any one of claims 1-10, wherein the composition has a gel time of about 14 hours to about 22 hours at a temperature of 21 C.
12. The curable composition of any one of claims 1-11, wherein the composition has a gel time of about 16 hours to about 20 hours at a temperature of 21 C.
13. 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, (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.
(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.
14. The method of claim 13, wherein at least one of the one or more curing agents is of Formula (I):
R1 _____________________________________ R2 H Xe OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-C10 alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 H Xe OH
(I) wherein A is ¨0¨, ¨CH2¨, or ¨NR'¨, R' is hydrogen or an optionally substituted Ci-Cio alkyl or C2-C10 alkenyl group; R is a Ci-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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-Cio aryl; and X is a carboxylate anion.
15. The method of claim 13 or 14, wherein at least one of the one or more curing agents is of Formula (II):
R1 _____________________________________ R2 H/NI X
OH
(II) wherein 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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
R1 _____________________________________ R2 H/NI X
OH
(II) wherein 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 Ci-C2o alkyl, C2-C2o alkenyl, Ci-C2o haloalkyl, C2-C2o haloalkenyl, or C6-C10 aryl; and X is a carboxylate anion.
16. The method of any one of claims 13-15, wherein at least one of the one or more curing agents is of Formula (III):
R1 _____________________________________ R2 xe OH
(III) wherein 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.
R1 _____________________________________ R2 xe OH
(III) wherein 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.
17. The method of any one of claims 13-16, wherein 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 14:1.
18. The method of any one of claims 13-17, wherein the ratio of the weight percentage of the resin to the weight percentage of the curing agent or curing agents is about 12:1.
19. The method of any one of claims 13-18, wherein the cured-in-place liner is heated to a temperature of at least about 85 C.
20. The method of any one of claims 13-18, wherein the cured-in-place liner is heated to a temperature of about 60 C to about 85 C.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2018/050008 WO2020050858A1 (en) | 2018-09-07 | 2018-09-07 | Curable composition for cured in place pipes |
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CA3111761A1 true CA3111761A1 (en) | 2020-03-12 |
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CA3111761A Pending CA3111761A1 (en) | 2018-09-07 | 2018-09-07 | Curable composition for cured in place pipes |
Country Status (6)
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EP (1) | EP3847204A1 (en) |
JP (2) | JP7281222B2 (en) |
AU (2) | AU2018440151B2 (en) |
CA (1) | CA3111761A1 (en) |
MX (1) | MX2021002470A (en) |
WO (1) | WO2020050858A1 (en) |
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US10696839B2 (en) | 2018-09-07 | 2020-06-30 | Pipefusion Cipp Corporation | Curable composition for cured in place pipes |
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US3792016A (en) * | 1972-01-06 | 1974-02-12 | Minnesota Mining & Mfg | Metal imidazolate-catalyzed systems |
JP2915094B2 (en) * | 1990-06-12 | 1999-07-05 | 新日鐵化学株式会社 | Pipe line lining method |
US20070116961A1 (en) * | 2005-11-23 | 2007-05-24 | 3M Innovative Properties Company | Anisotropic conductive adhesive compositions |
CN101679599B (en) * | 2007-06-13 | 2013-01-09 | 巴斯夫欧洲公司 | Catalyst for curing epoxides |
US20100227981A1 (en) * | 2009-03-04 | 2010-09-09 | Air Products And Chemicals, Inc. | Epoxide-based composition |
US9080007B2 (en) * | 2013-02-28 | 2015-07-14 | Air Products And Chemicals, Inc. | Anhydride accelerators for epoxy resin systems |
EP2981565B1 (en) * | 2013-04-05 | 2017-10-04 | Evonik Degussa GmbH | One component epoxy curing agents comprising hydroxyalkylamino cycloalkanes |
WO2018118137A1 (en) * | 2016-12-21 | 2018-06-28 | Evonik Degussa Gmbh | N-hydxyl ethyl pipridine (nhep): a novel curing agent for epoxy systems |
-
2018
- 2018-09-07 AU AU2018440151A patent/AU2018440151B2/en active Active
- 2018-09-07 JP JP2021512921A patent/JP7281222B2/en active Active
- 2018-09-07 WO PCT/US2018/050008 patent/WO2020050858A1/en unknown
- 2018-09-07 CA CA3111761A patent/CA3111761A1/en active Pending
- 2018-09-07 MX MX2021002470A patent/MX2021002470A/en unknown
- 2018-09-07 EP EP18789272.4A patent/EP3847204A1/en active Pending
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- 2023-05-08 JP JP2023076640A patent/JP2023113624A/en active Pending
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EP3847204A1 (en) | 2021-07-14 |
JP2022503662A (en) | 2022-01-12 |
AU2024204145A1 (en) | 2024-07-04 |
MX2021002470A (en) | 2021-04-29 |
WO2020050858A1 (en) | 2020-03-12 |
JP7281222B2 (en) | 2023-05-25 |
AU2018440151A1 (en) | 2021-03-25 |
AU2018440151B2 (en) | 2024-04-18 |
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