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WO1996018684A1 - Composition en epoxy pour pipelines et sa methode de fabrication - Google Patents

Composition en epoxy pour pipelines et sa methode de fabrication Download PDF

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Publication number
WO1996018684A1
WO1996018684A1 PCT/US1995/016541 US9516541W WO9618684A1 WO 1996018684 A1 WO1996018684 A1 WO 1996018684A1 US 9516541 W US9516541 W US 9516541W WO 9618684 A1 WO9618684 A1 WO 9618684A1
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WO
WIPO (PCT)
Prior art keywords
polymer
mole
pipelining
curing agent
aliphatic
Prior art date
Application number
PCT/US1995/016541
Other languages
English (en)
Inventor
Robert F. Brady, Jr.
James D. Adkins
Original Assignee
The Government Of The United States Of America,
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/355,481 external-priority patent/US5919713A/en
Application filed by The Government Of The United States Of America, filed Critical The Government Of The United States Of America,
Publication of WO1996018684A1 publication Critical patent/WO1996018684A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/146—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies to metallic pipes or tubes
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/54—Amino amides>
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68359—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used as a support during manufacture of interconnect decals or build up layers

Definitions

  • This invention relates to a pipelining network polymer composition for the in situ rehabilitation of pipes.
  • the pipelining network polymer composition is used as a lining which protects pipes or other surfaces from corrosion and erosion.
  • the pipelining composition forms a barrier which prevents the leaching of, for example, metals from pipes.
  • This invention further relates to a pipelining composition suitable for use in the rehabilitation of pipes used for transporting fluids such as drinking water.
  • This invention more particularly, relates to an epoxy resin/curing agent corrosion-resistant network pipelining composition suitable for the in situ rehabilitation and life extension of pipes wherein the pipelining composition has sufficient adhesion (i.e. pass 40 inch-pound ASTM D-2794 test) and a sufficiently quick drying time (e.g. about 50 to about 60 minutes or less) to avoid excessive sagging of the pipelining prior to cure.
  • Copper-nickel alloys such as those used in shipboard piping systems, are rapidly destroyed by hydrochloric acid, hydrogen sulfide, sulfuric acid, and other corrosive products of bacterial activity. Excessively high flow rates also erode the metal, thereby causing loss of wall thickness, the leaching of metals into the fluids flowing through such pipes and eventual perforation through the pipe. Contamination is
  • An impervious lining serves as a barrier keeping harmful materials, such as lead, from contaminating fluids or other materials carried by such pipes, and extends the useful life of such pipes.
  • Underground fluid-transporting pipes fracture and corrode with use and age. Repair of a leaking pipe requires excavation, repair and/or replacement of the damaged pipe. This method of replacement or patching of leaks can be very expensive and time consuming. If access to the pipe is blocked by overground structures, excavation of pipes becomes difficult. If the exterior of pipes is coated with asbestos, replacement and/or removal of the asbestos is prohibitively expensive.
  • the use of a suitable corrosion-resistant pipelining network polymer composition would obviate the need to excavate aging pipes because such pipes would be amenable to in situ rehabilitation.
  • Epoxy linings have been formulated for use as linings for the interior of pipes.
  • the coatings are suitable for pipes which are made of metallic or non- metallic materials and which carry gases, liquids and slurries of solids suspended in fluids.
  • a lining known as Naval Research Laboratory formula 4A i.e. NRL formula 4A or just 4A
  • NRL formula 4A has been used for lining pipes in aircraft carriers since 1988.
  • NRL formula 4A is sensitive to contaminants on the pipe surface to be coated, linings of 4A in pipes sometimes show craters and other film defects.
  • NRL formula 4A is formulated using an oligomeric methylene dianiline (MDA) derivative as the curing agent.
  • MDA oligomeric methylene dianiline
  • any new pipelining formulation be at least as effective as the NRL formula 4A lining.
  • an epoxy pipelining network polymer which optionally may contain a variety of colors or pigments that allow the applicator to distinguish between successive layers of pipelining network polymer coatings.
  • a pipelining that is made only of the epoxy resin and the curing agent blend. If necessary, a thixotropic agent and/or a pigment may optionally be added to impart a desired viscosity and/or a desired color, respectively.
  • This invention relates to epoxy pipelining formulations that impart both practical and optimal properties to the resulting lining.
  • Typical pipelining formulations include by weight specific percentages of curing agent blends and epoxy resins.
  • Preferable formulations include by weight specific percentages of epoxy resins and curing agent blends having viscosity control agents (thixotropic agents).
  • Most preferable formulations include by weight specific percentages of epoxy resins curing agent blends having both viscosity control agents (thixotropic agents) and pigments.
  • the curing agent blend is further described as comprising an amine curing agent, a polyamide curing agent and a polyamide cyclized curing agent.
  • Polyalkylene amine curing agents are manufactured by the reaction of ethylene and ammonia. It is recognized that a mixture of isomers is produced in this operation as well.
  • the products include linear molecules such as ethylene diamine
  • the amine curing agents may be selected from the group consisting of ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetraamine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA) and aminoethyl piperazine (AEP).
  • EDA ethylene diamine
  • DETA diethylene triamine
  • TETA triethylene tetraamine
  • TEPA tetraethylene pentamine
  • PEHA pentaethylene hexamine
  • AEP aminoethyl piperazine
  • the linear amine curing agents EDA, DETA, TETA, TEPA and PEHA generally have the structure:
  • n is an integer equal to 0, 1, 2, 3 or 4, respectively.
  • amine curing agents typically, have the formula R' ⁇ NH 2 wherein R' is a saturated hydrocarbon group of 1-25 carbon atoms.
  • the amine curing agent may be a diamino compound having the structure:
  • An exemplary diamino curing agent is 1,2-diaminocyclohexane (1,2-DCH) having the formula:
  • the polyamide curing agents are formed by reacting carboxylic acids with primary or secondary amines.
  • the carboxylic acids reacted with amine curing agents to form the respective amidoamine (and imidazoline curing agents discussed, infra) curing agents may be mono acids or dimer acids having the formula RCOOH or HOOCRCOOH, respectively.
  • the R group is a saturated hydrocarbon group of 1-36 carbon atoms.
  • Examples of monoacids used to react with an amine curing agent to form the respective amidoamine curing agent (and the imidazoline curing agent discussed, infra) may be selected from the group consisting of methanoic acid (formic acid, HCOOH), ethanoic acid (acetic acid, CH 3 C0 2 H), propanoic acid (propionic acid, CH 3 CH 2 C0 2 H), butanoic acid (butyric acid, CH 3 (CH 2 ) 2 C0 2 H), pentanoic acid (valeric acid, CH 3 (CH 2 ) 3 C0 2 H), hexanoic acid (caproic acid,CH 3 (CH 2 ) 4 C0 2 H), heptanoic acid (enanthic acid, CH 3 (CH 2 ) s C0 2 H), octanoic acid (caprylic acid, CH 3 (CH 2 ) 6 C0 2 H), nonanoic acid (pelargonic acid, CH 3 (CH 2 ) 7 C
  • R, R ⁇ R 1 and R 2 are saturated hydrocarbon groups of 1 to 25 carbon atoms, inclusive.
  • R', R 1 and R 2 may be saturated alkyl amino compounds such as EDA, DETA, TETA, TEPA, PEHA and AEP etc. of 2-25 carbon atoms, inclusive.
  • the cyclized polyamide curing agent (also referred to as the imidazoline curing agent) is manufactured in three steps from three basic raw materials.
  • Fatty acids typically, obtained from a variety of vegetable sources such as tung, tall, soya, or safflower oil are dimerized and the resultant dimer acids are reduced with hydrogen to their fully saturated analogs.
  • the fatty acids may be reduced without dimerization, or a blend of the reduced dimer acids and the non- dimerized reduced fatty acids may be employed. It is recognized that a mixture of isomers is produced in all these operations.
  • the acids are reacted with polyalkylamines to form polyamide curing agents which are further dehydrated to form the imidazoline curing agents.
  • the imidazoline curing agents formed typically, have the formulas:
  • n 0, 1, 2, 3, or 4 and wherein R, R', R 1 and R 2 are saturated hydrocarbon groups of 1 to 25 carbon atoms, inclusive, and R 1 and R 2 may alternatively be a H atom.
  • R', R 1 and R 2 may be saturated alkyl amino compounds such as EDA, DETA, TETA, TEPA, PEHA and AEP etc. of 2-25 carbon atoms, inclusive.
  • the imidazoline curing agents have several valuable properties which are important for the production of pipelinings.
  • the mild alkaline nature of the exemplary imidazoline curing agent such as (2), infra, passivates metals and retards
  • the exemplary imidazoline curing agent (2), infra possesses a long nonpolar hydrocarbon chain ⁇ — R ⁇ and also a polar imidazoline ring; thus, it has the properties of a surfactant.
  • Such an exemplary imidazoline curing agent such as (2), infra is able to lift dirt, oil and other impurities from the surface to be coated, enabling a wet film to spread evenly over the surface to be coated.
  • an exemplary surface to be coated is a Cu-Ni alloy having a 70 (Cu)/30 (Ni) or 90(Cu)/10 (Ni) composition.
  • the reduced dimer acid, reduced fatty acid, or blend of acids e.g. compound (la), infra
  • the exemplary mixture of polyalkylene amines e.g. compound (3a), infra
  • Reaction between one acid group and one primary or secondary amine leads to the elimination of a molecule of water and the formation of an amide linkage (e.g. as shown in exemplary compounds (4) and (4a), infra).
  • a primary or secondary amine which is two carbon atoms removed from the amide nitrogen reacts with the amide carbonyl oxygen, a second molecule of water is removed and an imidazoline ring is formed as seen in exemplary compounds (2) and (2a), infra.
  • the curing agent blend comprises an amine curing agent, a polyamide cyclized curing agent (also referred to as an imidazoline curing agent) and a polyamide curing agent (also referred to as an amidoamine curing agent).
  • the curing agent blend may further comprise benzyl alcohol (e.g.
  • the curing agent blend may further comprise (along with the amine curing agent, the imidazoline curing agent, the amidoamine curing agent and the unreacted mono and dimer acids) one or more pigments, one or more viscosity controlling agents and a small amount of one or more epoxy resins.
  • the curing agent blend comprises one or more amine curing agents, one or more imidazoline curing agents, one or more amidoamine curing agents and one or more reactive diluents. More typically, the curing agent blend comprises one or more amine curing agents, one or more imidazoline curing agents, one or more amidoamine curing agents, one or more reactive diluents and a small amount of one or more epoxy resins. Most typically, the curing agent blend comprises one or more amine curing agents, one or more imidazoline curing agents, one or more amidoamine curing agents, one or more reactive diluents, a small amount of one or more epoxy resins and one or more pigments.
  • the curing agent blend comprises one or more amine curing agents, one or more imidazoline curing agents, one or more amidoamine curing agents, one or more reactive diluents, a small amount of one or more epoxy resins, one or more pigments and one or more viscosity controlling agents.
  • the curing agent blend may comprise one or more amine curing agents, one or more imidazoline curing agents, one or more amidoamine curing agents, one or more reactive diluents and a small amount of one or more epoxy resins.
  • the optional pigment and/or the optional viscosity controlling agents may preferably be added to the epoxy resin component (component A, infra, at Example 1) instead of to the curing agent blend component (component B, infra, at Example 1).
  • the curing agent blend may comprise 1,2- diaminocyclokexane (1,2-DCH) as the amine curing agent, one or more imidazoline curing agents, one or more amidoamine curing agents, benzyl alcohol as a reactive diluent, and a small amount of an epoxy resin such as DGEBA (the diglycidyl ether of bisphenol A; see infra page 38) and/or DGEBF (the diglycidyl ether of bisphenol
  • an exemplary curing agent blend comprises about 1-70 mole % of the amine curing agent, about 0.1-40 mole % of the imidazoline, about 5-95 mole % of the amidoamine, about 0-35 mole % of the reactive diluent, and about 0-10 mole % of the epoxy resin, inclusive, respectively. More typically, an exemplary curing agent blend comprises about 2-69 mole % of the amine curing agent, about 0.5-35 mole % of the imidazoline, about 6-90 mole % of the amidoamine, about 2-30 mole % of the reactive diluent, and about 0-9 mole % of the epoxy resin, inclusive, respectively. Most typically, an exemplary curing agent blend comprises about 3-68 mole % of the amine curing agent, about 0.75-30 mole
  • an exemplary curing agent blend comprises about 4-67 mole % of the amine curing agent, about 0.8-25 mole % of the imidazoline, about 8- 84 mole % of the amidoamine, about 4-24 mole % of the reactive diluent, and about 0-7 mole % of the epoxy resin, inclusive, respectively.
  • an exemplary curing agent blend comprises about 5-66 mole % of the amine curing agent, about 0.9-22 mole % of the imidazoline, about 9-83 mole % of the amidoamine, about 5-23 mole % of the reactive diluent, and about 0-6 mole % of the epoxy resin, inclusive, respectively.
  • an exemplary curing agent blend comprises about 6-65 mole % of the amine curing agent, about 1.0-20 mole % of the imidazoline, about 10-80 mole % of the amidoamine, about 6-20 mole % of the reactive diluent, and about 0-5 mole % of the epoxy resin, inclusive, respectively.
  • Composition of pipelinings can be made from a mixture of the part A epoxy resin (DGEBA: Epon * 828, and/or Araldite XU Bis F GY * 281) containing optional pigments such as Titanium Oxide (Ti0 2 R-960 * ), red iron oxide (Red Iron Oxide RO-6097 * ), phthalocyanine blue and/or phthalocyanine green and optional viscosity controlling agents such as silicon dioxide (Cab-O-Sil TS-720 * Cab-O-Sil R 974 * ) and a part B curing agent blend.
  • Each primary and/or secondary amine nitrogen atom marked with an asterisk (*) on the exemplary pipelining products (5) - (13), inclusive, can further react with the methylene carbon atom (i.e.-CHOCH 2 ) of an available epoxide ring originally from, for example, the diglycidyl ether of Bisphenol A (DGEBA) or the diglycidyl ether of Bisphenol F (DGEBF) wherein a new -C-N- bond is formed.
  • DGEBA diglycidyl ether of Bisphenol A
  • DGEBF diglycidyl ether of Bisphenol F
  • the cross-linked network polymer has one or more cross-linking -C-N- bonds and the cross-linked network polymer forms the pipelining network polymer which is the subject invention of this patent application.
  • the reaction product of exemplary reactants (1), (2), (3) and (4) is an exemplary cross-linked network polymer of one or more of (5), (6), (7), (8), (9), (10), (11), (12), (13) and (others).
  • another exemplary network polymer may be formed by the reaction of exemplary reactants (1), (2), (3a) and (4)-- ⁇ reaction not schematically shown ⁇ .
  • Another exemplary network polymer may be formed by the reaction of exemplary reactants (1), (2), (3), (3a) and (4)— ⁇ reaction not schematically shown ⁇ .
  • Yet another exemplary network polymer may be formed by the reaction of exemplary reactants (1), (2), (2a), (3), (3a), (4) and/or (4a) -- ⁇ reaction not schematically
  • cross-linked network polymer variations can be drawn which are within the scope of the present inventive discovery. However, it is sufficient to describe these cross-linked network polymer variations to include cross-linking bonds between the primary and/or secondary nitrogen atoms of the curing agent blend (i.e. the curing agent blend comprising the amine curing agent, the amidoamine curing agent and the imidazoline curing agent) and the methylene carbon atoms from the epoxy resin on the epoxide ring (i.e. the oxirane ring -CHOCH 2 ).
  • the curing agent blend i.e. the curing agent blend comprising the amine curing agent, the amidoamine curing agent and the imidazoline curing agent
  • methylene carbon atoms from the epoxy resin on the epoxide ring i.e. the oxirane ring -CHOCH 2
  • the curing agent blend comprising the amine curing agent, the imidazoline curing agent and the amidoamine curing agent has an amine gram equivalent weight (AEW) per active amine between about 90 to about 800 grams. More typically, the curing agent blend has an AEW per active amine between about 95 to about 400 grams. Most typically, the curing agent blend has an AEW per active amine between about 100 to about 200 grams. Preferably, the curing agent blend has an AEW per active amine between about 110 to about 180 grams. More preferably, the curing agent blend has an AEW per active amine between about 120 to about 170 grams. Most preferably, the curing agent blend has an AEW per active amine between about 130 to about 160 grams.
  • AEW amine gram equivalent weight
  • the curing agent blend must contain both polar and nonpolar moieties. These moieties provide surfactant properties to the pipelining formulation. The surfactant properties are necessary to ensure that the resulting lining will have the necessary tolerance for oils, dirt and other imperfections present on the pipe surface or other surface to be coated with the pipelining.
  • a solvent such as benzyl alcohol (C 6 H 5 CH 2 OH) may be used as a reactive diluent.
  • the exemplary benzyl alcohol reactive diluent is added to the curing agent blend.
  • the diluent is present in an amount to comprise 0 to 35 percent by weight of the final cured exemplary pipelining network polymer product (also referred to as pipelining) of one or more of (5) - (13), inclusive.
  • the exemplary benzyl alcohol reactive diluent is used in order to dilute and/or adjust the viscosity of the homogeneous final mixture of epoxy resin and the curing agent blend.
  • Benzyl alcohol is a valuable diluent because it reacts with glycidyl ether becoming covalently joined to the pipelining network polymer product. Therefore, the benzyl alcohol does not evaporate into the atmosphere as an objectionable volatile organic compound (VOC).
  • Other additives such as nonylphenol may be added in small amounts less than about 5 percent by weight of the final cured pipelining network polymer product.
  • Nonylphenol like benzyl alcohol, is optionally added to the exemplary curing agent blend at a level of 0-5 percent by weight of the final cured exemplary pipelining network polymer product. The final cured
  • pipelining network polymer product is recognized to be a mixture of isomers (e.g. an exemplary mixture of the network polymer of one or more of (5) - (13), inclusive, and may contain unreacted acids, for example, (la) and amines, for example, (2), (3), (3a), (4) and (4a)).
  • isomers e.g. an exemplary mixture of the network polymer of one or more of (5) - (13), inclusive, and may contain unreacted acids, for example, (la) and amines, for example, (2), (3), (3a), (4) and (4a)).
  • the imidazoline component, for example (2), of the curing agent blend is more miscible with the exemplary diglycidyl ether (1) than is the exemplary uncyclized polyamide (4), another component of the exemplary curing agent blend.
  • the reaction product e.g. the network polymer of one or more of (5) - (13), inclusive
  • the epoxy resin to the surface (e.g. any metallic or non-metallic surface) to be coated.
  • the induction time is between about 0 to 50 minutes. More typically, the induction time is between about 1 to 45 minutes. Most typically, the induction time is between about 2 to 30 minutes. Preferably, the induction time is between about 3 to 20 minutes. More preferably, the induction time is between about 4 to 15 minutes. Most preferably, the induction is between about 5 to 10 minutes.
  • the reaction mixture i.e. reaction mixture of the curing agent blend and the epoxy resin
  • the optimal pot life is about 1 hour because this is about the amount of time needed to apply the formed pipelining on the interior of pipes.
  • a long pot life results in a thick coating being deposited at the bottom of the pipe and a relatively thin coating being deposited at the top and sides of the pipe.
  • a pot life of less than about 1 hour results in the hardening of the pipelining while the pipelining is being applied to the interior surface of a pipe. Therefore, a pot life of less than about 1 hour creates problems in the application of the pipelining.
  • a pot life sufficiently long to allow complete application and sufficiently short to allow drying (hardening) to prevent excessive running (due to gravity) is sought.
  • a suitable pot life is between about 1.0 - 4.0 hours. More typically, a suitable pot life is between about 1.0 - 3.5 hours. Most typically, a suitable pot life is between about 1.0 - 3.0 hours. Preferably, a suitable pot life is between about 1.0 - 2.75 hours.
  • a suitable pot life is between about 1.0 - 2.50 hours. Most preferably, a suitable pot life is between about 1.0 - 2.25 hours.
  • the curing agent blend is chosen to have other specific properties.
  • the mixed viscosity (viscosity of the homogeneous mixture of curing agent blend and epoxy resin prior to cure), typically, should be between about 350 - 1000 centipoise.
  • the mixed viscosity more typically, should be between about 375 - 900 centipoise (cps). Most typically, the mixed viscosity of the lining should be between about 400 - 800 cps.
  • the mixed viscosity of the lining should be between about 415 - 750 cps. More preferably, the mixed viscosity of the lining should be between about 425 - 725 cps. Most preferably, the mixed viscosity of the lining should be between about 440 - 700 cps.
  • NRL formula 4A had been used for lining pipes in aircraft carriers since 1988.
  • the epoxy resin used in NRL formula 4A was DGEBA (3a) and the curing agent was oligomeric methylene dianiline (MDA) having the formula:
  • n 1, 2, 3, 4, 5, or 6
  • NRL formula 4A was prepared according to the following method. Typically, NRL formula 4A is manufactured in two separate parts, part A comprising a pigmented epoxy resin and part B comprising a curing agent. Parts A and B are not combined until just before the pipelining is to be applied.
  • part A of pipelining 4A was manufactured by mixing all of the liquid epoxy resin (3a), all of an optional pigment such as iron oxide and all of an optional viscosity controlling agent such as fumed silica in a high speed disperser or a 3-roll mill until the mixture (part A) was uniformly mixed and the optional
  • pigments were ground to a fineness of at least 4 on the Hegman Scale, as measured by the ASTM standard test method D1210-79, Fineness of Dispersion of Pigmented- Vehicle Systems.
  • Part B consisted only of the curing agent (i.e. MDA) which was used as received.
  • the 4A pipelining was made by thoroughly stirring parts A and B separately until each was homogeneous. Thereafter, the two parts A and B were combined and blended until the mixture was homogeneous. The mixture remained fluid for about one hour after blending. The mixture must be applied while it remained fluid. After about one hour, the mixture became extremely viscous and could not be applied in the non-fluid state. Complete cure was achieved after several days at 50°F or above.
  • MDA is available from Ciba-Geigy under the designation Ciba-Geigy HY2969 * .
  • Exemplary suitable epoxy resins may have the following structures:
  • R 3 R 4 - H R 3 - H ; R 4 - CH 3 (DGEBE)
  • Exemplary epoxy resins are the diglycidyl ethers derived from phenol such as
  • R CH 3 , or CH 2 CH 3 , or CH 2 CH 2 CH 3
  • R 8 CH 3 , or CH 2 CH3 , or CH 2 CH 2 CH 3
  • DGEBA and DGEBF among others.
  • a variety of epoxy resins that satisfy the above requirements are commercially and include products such as Epon 828TM available from Shell.
  • the suitable epoxy resin has an equivalent weight per epoxide unit of between about 150 to 950 grams. More typically, the suitable epoxy resin has an equivalent weight per epoxide unit of between about 155 to 900 grams. Most typically, the suitable epoxy resin has an equivalent weight per epoxide unit of between about 160 to 800 grams. Preferably, the suitable epoxy resin has an equivalent weight per epoxide unit of between about 165 to 700 grams. More preferably, the suitable epoxy resin has an equivalent weight per epoxide unit of between about 170 to 600 grams. Even more preferably, the suitable epoxy resin has an equivalent weight per epoxide unit of between about 175 to 500 grams. Most preferably, the suitable epoxy resin has an equivalent weight per epoxide unit of between about 180 to 195 grams.
  • the optional pigment may be used to give color to the pipelining network polymer formed by the reaction between the curing agent blend and an epoxy resin.
  • An iron oxide pigment is a synthetic red iron oxide pigment containing a minimum of 93 percent of ferric oxide and conforming to American Society for Testing and Materials (ASTM) standard specification D3721-83.
  • the color imparted by the iron oxide pigment is preferably sufficiently opaque so that a 75 micrometer thick film containing 4.0 percent or more of the pigment completely hides the surface being covered.
  • the pigment is insoluble in water, non-fading and chemically stable.
  • the oil absorption of the iron oxide pigment is between about 10 to 60 pounds of oil per hundred pounds of pigment. More typically, the oil absorption of the pigment is between about 11 to 50 pounds of oil per hundred pounds of pigment. Most typically, the oil absorption of the pigment is between about 12 to 40 pounds of oil per hundred pounds of pigment. Preferably, the oil absorption of the pigment is between about 13 to 30 pounds of oil per hundred pounds of pigment. More preferably, the oil absorption of the pigment is between about 14 to 25 pounds of oil per hundred pounds of pigment. Most preferably, the oil absorption of the pigment is between about 16 to 20 pounds of oil per hundred pounds of pigment.
  • the density of the iron oxide pigment is between about 34 to 47 pounds per gallon. More typically, the density of the iron oxide pigment is between about 36 to 45 pounds per gallon. Most typically, the density of the iron oxide pigment is between about 38 to 43 pounds per gallon. Preferably, the density of the iron oxide pigment is between about 39 to 42 pounds per gallon. More preferably, the density of the iron oxide pigment is between about 40 to 41.5 pounds per gallon. Most preferably, the density of the iron oxide pigment is between about 40.6 to 41.0 pounds per gallon.
  • Suitable exemplary red iron oxide pigments include the following: Red Iron Oxide RO-6097TM from Pfizer, Inc.
  • the pigment is rutile titanium dioxide pigment containing a minimum of 80 percent of titanium dioxide and conforming to Type IV of the ASTM standard specification D476-84.
  • the titanium dioxide pigment is bright white in color and is sufficiently opaque so that a 75 micrometer thick film containing 4.0 percent or more of the pigment completely hides the surface being covered.
  • the pigment is insoluble in water, non-fading and
  • the oil absorption of the titanium dioxide pigment is between about 14 to 45 pounds of oil per hundred pounds of pigment. More typically, the oil absorption of the pigment is between about 14.2 to 40 pounds of oil per hundred pounds of pigment. Most typically, the oil absorption of the pigment is between about 14.4 to 30 pounds of oil per hundred pounds of pigment.
  • the oil abso ⁇ tion of the pigment is between about 14.6 to 20 pounds of oil per hundred pounds of pigment. More preferably, the oil abso ⁇ tion of the pigment is between about 15 to 19 pounds of oil per hundred pounds of pigment. Most preferably, the oil absorption of the pigment is between about 16 to 18 pounds of oil per hundred pounds of pigment.
  • the density of the titanium dioxide pigment is between about 24 to 41 pounds per gallon. More typically, the density of the titanium dioxide pigment is between about 26 to 39 pounds per gallon. Most typically, the density of the titanium dioxide pigment is between about 28 to 37 pounds per gallon. Preferably, the density of the titanium dioxide pigment is between about 30 to 35 pounds per gallon. More preferably, the density of the titanium dioxide pigment is between about 31 to 34 pounds per gallon. Most preferably, the density of the titanium dioxide pigment is between about 31.5 to 33.5 pounds per gallon.
  • Suitable exemplary titanium dioxide pigments include the following: Ti0 2 R-960 TiPureTM available from E.I. Dupont Nemours, Inc.
  • Suitable exemplary pigments may be selected from the group consisting of phthalocyanine blue and phthalocyanine green and mixtures thereof.
  • the pigments suitable for use with the present invention are the non-toxic pigments (i.e. do not leach out metals such as lead or other toxic materials).
  • a number or other visible color pigments may be used, for example, the white pigments (e.g. Titanium Dioxide-Rutile, Titanium Dioxide-Ana tase), extender pigments (e.g. Calcium Carbonate, Silica, Other Silicas, Talc, China Clay, Clay, Mica), Iron Oxide Pigments (e.g. Yellow Iron Oxide, Brown Iron Oxide, Black Iron Oxide), Red Pigments (e.g.
  • the viscosity controlling agents are selected to have specific properties.
  • the thixotropic agent is a hydrophobic fumed silica containing a minimum of 98 percent of silicon dioxide.
  • the thixotropic agent is insoluble in water and chemically stable.
  • the thixotropic agent has a
  • the thixotropic agent has a (BET) ASTM C-819 surface area of between about 80 to 300 square meters per gram. More typically, the thixotropic agent has a (BET) ASTM C-819 surface area of between about 82 to 200 square meters per gram. Most typically, the thixotropic agent has a (BET) ASTM C-819 surface area of between about 84 to 150 square meters per gram. Preferably, the thixotropic agent has a (BET) ASTM C-819 surface area of between about 86 to 125 square meters per gram. More preferably, the thixotropic agent has a (BET) ASTM C-819 surface area of between about 88 to 120 square meters per gram. Most preferably, the thixotropic agent has a (BET) ASTM C-819 surface area of between about 90
  • the density of the thixotropic agent is between about 10 to 20 pounds per gallon. More typically, the density of the thixotropic agent is between about 11 to 19 pounds per gallon. Most typically, the density of the thixotropic agent is between about 12 to 18 pounds per gallon. Preferably, the density of the thixotropic agent is between about 13 to 17 pounds per gallon. More preferably, the density of the thixotropic agent is between about 13.5 to 16.5 pounds per gallon. Most preferably, the density of the thixotropic agent is between about 15 to 16 pounds per gallon.
  • Suitable exemplary thixotropic agents may be selected from the group consisting of Cab-O-Sil TS-720TM, Cab-O-Sil R 974TM, each available from Cabot Co ⁇ ., hydrophobic fumed silica and mixtures thereof.
  • Other suitable thixotropic agents listed in National Paint and Coatings Association Raw Materials Index complying with the above stated properties are suitable for use with the present invention and are inco ⁇ orated herein by reference in their entirety for all purposes.
  • EXAMPLE 1 Add epoxy resin (e.g. Epon 828 from Shell Chemical Company, 500gm) to a lOOOmL steel beaker equipped with a high speed paint agitator (Cowles type mixing blade). While stirring the epoxy resin at about 2000 revolutions per minute, slowly add 77.5 grams of red iron oxide pigment (e.g. Fe 2 0 3 ; R-6097 from Pfizer Inc. is a suitable iron oxide pigment) over a period of 2-3 minutes. Immediately thereafter, add 0.52 grams of fumed silica (e.g. Cab-O-Sil TS-720 from Cabot Co ⁇ .) to the agitating mixture of epoxy resin and iron oxide.
  • red iron oxide pigment e.g. Fe 2 0 3 ; R-6097 from Pfizer Inc. is a suitable iron oxide pigment
  • fumed silica e.g. Cab-O-Sil TS-720 from Cabot Co ⁇ .
  • An exemplary Cu-Ni alloy pipe having a length of about 20 to 30 feet and an inner diameter of 2 inches may be coated with the homogeneous mixture of Components A and B. Pre-treat by sand blasting the inner surface of the exemplary Cu-Ni alloy pipe to be coated with garnet grit (20-30 mesh; Idaho garnet sand is preferred) sand followed by drying with dry air.
  • All mixing is to be done at standard temperature and pressure of about 1 atmosphere and 25 degrees Celsius. After achieving complete mixing and allowing the mixture (of Components A and B) to stand for 5 - 10 minutes, apply the homogeneous mixture of Component A and Component B to the inner surface of a Cu-Ni alloy pipe using an air stream to cause the homogeneous mixture of Component A and Component B to coat the inner surface of the pipe.
  • a total coating thickness of about 12 mils at the top and of about 20 mils at the bottom inner surfaces should be achieved.
  • EXAMPLE 2 An exemplary curing agent blend was prepared by reacting palmitic acid,
  • the exemplary curing agent blend was prepared as follows:
  • Palmitic acid solid; 24.7 gm.; 0.0963 moles; C 16 H 32 0 2
  • a magnetic stirrer was placed in an Erlenmeyer flask containing a magnetic stirrer and connected to a condenser with a Dean-Stark trap.
  • step (b) 1,2-diaminocyclohexane (liquid; 11.8 gm.; 0.1033 moles; C 6 H, 4 N 2 ) was placed in the flask from step (a) and the reaction mixture was heated to 170 °C over 10 - 20 minutes on a hot plate. As the palmitic acid melted into a liquid, the reaction mixture was stirred using a Teflon- coated magnetic stirrer. Stirring and continuous heating at 170 °C was carried out for 4 hours while about 1.8 grams of water (about 0.0999 moles H 2 0) was collected by the Dean-Stark trap.
  • benzyl alcohol liquid; 9.4gm; 0.0869 moles; HgO
  • 1,2 diaminocyclohexane liquid; 30 gm.; 0.2627 moles; C 6 H 14 N 2
  • Component B (liquid; 1.6 grams; 0.0140 moles; C 6 H I4 N 2 ) was added and mixed until a new homogeneous mixture was obtained. This final mixture formed the desired exemplary curing agent blend referred to as Component B.
  • step (e) of example 2 To 100 grams of Component A prepared according to Example 1, supra, 15.7 grams of Component B (step (e) of example 2) was added. The mixture of Component A (100 grams) and Component B (15.7 grams) was stirred until homogeneous. Thereafter, the mixture was allowed to induct for 10-15 minutes. Immediately thereafter, the inducted homogeneous mixture was applied to a steel plate using a paint brush to a thickness of about 10 to 15 mils. The film was allowed to dry for about 2.75 hours, at which time it was dry to touch.
  • the pot life of the mixture was between about 1.5 to about 1.8 hours, inclusive.
  • the film passed the 40 inch-pound direct impact ASTM D-2794 test.
  • the film showed chemical resistance to hot aqueous sodium hypochlorite and/or calcium hypochlorite (e.g. Chlorox TM) at 60°C for 7 days and to 7% by weight of hot sulfuric acid (e.g. at 60 °C) for 7 days.
  • the reaction steps of EXAMPLE 2 are depicted below:
  • An exemplary curing agent blend was prepared by reacting azelaic acid (nonanedioic acid), hexanoic acid, triethylene tetramine (NH 2 CH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 NH 2 ; TETA) and benzyl alcohol.
  • the exemplary curing agent blend was prepared as follows:
  • reaction mixture was poured into a beaker and allowed to cool to room temperature over 60-80 minutes.
  • This final mixture formed the desired exemplary curing agent blend referred to as Component B.
  • Component A Component A prepared according to Example 1, supra
  • the mixture of Component A and Component B was agitated for about 5 minutes to achieve a homogeneous mix.
  • the homogeneous mixture of Component A and Component B was allowed to stand for 5 - 10 minutes.
  • An exemplary sandblasted flat steel panel (6" by 6") was coated with the homogeneous mixture of Components A and B. All mixing was done at standard temperature and pressure of about 1 atmosphere and 25 °C.
  • the applied coating was dried for about 1 to 2 hours at room temperature and pressure. A total coating thickness of about 12 mils was obtained on the coated surface of the steel panel. After about 24 hours of drying time at room temperature and pressure, a fully intact cured coating was obtained on the steel panel.
  • the coated steel panel passed the 40 inch-pound ASTM D-2794 test.
  • the film exhibited chemical resistance to hot aqueous sodium hypochlorite and/or calcium hypochlorite (e.g. Chlorox TM) at 60°C for 7 days and to 7% by weight hot sulfuric acid (i.e. at 60 °C) for 7 days.
  • the reaction steps of EXAMPLE 3 are depicted below:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

Composition polymère réticulée pour réseau de pipelines destinée à la remise en état des canalisations in situ. La composition polymère comprend au moins une résine époxy liquide et une quantité efficace de mélange liquide d'agent de réticulation composé d'une polyamine aliphatique, d'une imidazoline aliphatique et d'une amidoamine aliphatique. La composition polymère peut encore comprendre un pigment, un diluant et/ou un agent de contrôle de la viscosité.
PCT/US1995/016541 1994-12-14 1995-12-14 Composition en epoxy pour pipelines et sa methode de fabrication WO1996018684A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/355,481 US5919713A (en) 1994-01-28 1994-12-14 Semiconductor device and method of making
US08/355,481 1994-12-14

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WO1996018684A1 true WO1996018684A1 (fr) 1996-06-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993639A (zh) * 2012-11-21 2013-03-27 中国石油天然气集团公司 管道修复用预浸料及制备与应用其的修复材料及修复方法
CN104513204A (zh) * 2013-09-26 2015-04-15 延安双丰集团有限公司 一种含三键咪唑啉类化合物及含三键咪唑啉类二氧化碳缓蚀剂及二氧化碳缓蚀剂的制备方法
WO2023006123A1 (fr) * 2021-07-27 2023-02-02 上海誉帆环境科技股份有限公司 Matériau de réparation in situ à température normale pour canalisation de drainage, et son procédé de construction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081168A (en) * 1990-05-30 1992-01-14 Shell Oil Company Epoxy resin system for insitu rehabilitation of pipes
US5192816A (en) * 1990-11-29 1993-03-09 Mitsui Petrochemical Industries, Ltd. Pipe inner surface coating composition
US5314023A (en) * 1993-01-19 1994-05-24 Dartez Terry R Method for selectively treating wells with a low viscosity epoxy resin-forming composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081168A (en) * 1990-05-30 1992-01-14 Shell Oil Company Epoxy resin system for insitu rehabilitation of pipes
US5192816A (en) * 1990-11-29 1993-03-09 Mitsui Petrochemical Industries, Ltd. Pipe inner surface coating composition
US5314023A (en) * 1993-01-19 1994-05-24 Dartez Terry R Method for selectively treating wells with a low viscosity epoxy resin-forming composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993639A (zh) * 2012-11-21 2013-03-27 中国石油天然气集团公司 管道修复用预浸料及制备与应用其的修复材料及修复方法
CN102993639B (zh) * 2012-11-21 2015-06-03 中国石油天然气集团公司 管道修复用预浸料及制备与应用其的修复材料及修复方法
CN104513204A (zh) * 2013-09-26 2015-04-15 延安双丰集团有限公司 一种含三键咪唑啉类化合物及含三键咪唑啉类二氧化碳缓蚀剂及二氧化碳缓蚀剂的制备方法
CN104513204B (zh) * 2013-09-26 2017-11-24 延安双丰集团有限公司 一种含三键双咪唑啉类化合物及含三键双咪唑啉类二氧化碳缓蚀剂及二氧化碳缓蚀剂的制备方法
WO2023006123A1 (fr) * 2021-07-27 2023-02-02 上海誉帆环境科技股份有限公司 Matériau de réparation in situ à température normale pour canalisation de drainage, et son procédé de construction

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