WO2017027199A1 - Matériaux époxy et leur utilisation dans des applications sous-marines - Google Patents

Matériaux époxy et leur utilisation dans des applications sous-marines Download PDF

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Publication number
WO2017027199A1
WO2017027199A1 PCT/US2016/044030 US2016044030W WO2017027199A1 WO 2017027199 A1 WO2017027199 A1 WO 2017027199A1 US 2016044030 W US2016044030 W US 2016044030W WO 2017027199 A1 WO2017027199 A1 WO 2017027199A1
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weight
epoxide
epoxy
equivalent
resins
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PCT/US2016/044030
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English (en)
Inventor
Rujul M. MEHTA
Mark W. Brown
Pankaj Gupta
Dwight D. Latham
Kamesh R. VYAKARANAM
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Dow Global Technologies Llc
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Publication of WO2017027199A1 publication Critical patent/WO2017027199A1/fr

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    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/14—Arrangements for the insulation of pipes or pipe systems
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)

Definitions

  • This invention relates to the field of insulated pipelines and structures, and in particular to the field of subsea pipelines and structures and pipelines for use in deep water.
  • Offshore oil drilling requires the conveyance of oil from underwater wellheads to shore or other surface installations for further distribution.
  • the resistance to flow of liquid products such as oil increases as temperature decreases.
  • the pipelines are generally insulated.
  • the underwater environment exposes equipment to compressive forces, near-freezing water temperatures, possible water absorption, salt water corrosion, undersea currents and marine life.
  • Polyurethanes are often used for insulating such subsea applications due to general ease of processing (two-component molding) and good mechanical properties (strong and tough elastomer).
  • insulation may suffer from hydrolytic degradation when exposed to hot-wet environments.
  • the oil temperature is high at the wellhead, there is a possibility of degradation of the polymer network if water were to ingress, which would negatively impact the insulation performance of the materials.
  • Polypropylene is another kind of material also used to insulate such pipelines, however; this requires a difficult application process, which is the extrusion of several layers, and such insulation generally does not possess the attractive mechanical properties of polyurethane.
  • Another proposed method of insulating undersea systems is the use of pre-cast sections of rigid epoxy- syntactic foam.
  • This material comprises a rigid epoxy resin mixed with a high volumetric proportion of hollow glass or ceramic spheres. Although this material exhibits excellent thermal conductivity, it is very brittle. Due to the rigidity and brittleness of this material, it is easily damaged when subjected to sudden impacts or high stress levels. To compound this problem, rigid epoxy-syntactic foams are difficult to repair. Removal or replacement of this material is extremely difficult because the sections are bonded to the surface using adhesives or mechanical fasteners.
  • This invention provides an amine cured epoxy thermoset material that combines the processing, mechanical flexibility, and adhesion properties of polyurethanes with the mechanical strength, thermal, and hydrolytic stability typically associated with epoxy materials.
  • thermoset is utilized to thermally insulate any object from a surrounding fluid.
  • thermoset is used to insulate undersea pipes and well head equipment from seawater.
  • the invention provides a method of thermally insulating an object from a surrounding fluid, the method comprising interposing the insulation material between the object and the fluid wherein the insulating material comprises the reaction product of (a) from 50 to 95 weight percent of an ambient temperature liquid epoxy-terminated prepolymer formed by reacting a polyoxyalkyleneamine having a molecular weight of from
  • R is the nucleus of an oxyalkylation-susceptible initiator containing 2-12 carbon atoms and 2 to 8 active hydrogen groups
  • U is an alkyl group containing 1-4 carbon atoms, preferably alkyl group containing 1 or 2 carbon groups
  • T and V are independently hydrogen, U, or preferably an alkyl group containing one carbon
  • n is number selected to provide a polyol having a molecular weight of 2,900 to 29,500
  • m is an integer of 2 to 8 corresponding to the number of active hydrogen
  • the first epoxide disclosed herein above is one or more of the formula
  • R 5 is C6 to ds substituted or unsubstituted aromatic, a d to Q aliphatic, or cycloaliphatic; or heterocyclic polyvalent group and b has an average value of from 1 to 8, preferably the epoxide is one or more of diglycidyl ethers of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (l, l-bis(4-hydroxylphenyl)-l-phenyl ethane), bisphenol F, bisphenol K, bisphenol S, tetrabromobisphenol A, phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol- hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins, dicyclopentadiene-substituted phenol resins tetramethylbiphenol,
  • the epoxide disclosed herein above is at least one cycloaliphatic first epoxide of the formula
  • R 5 is C 6 to ds substituted or unsubstituted aromatic, a d to Cs aliphatic, or cycloaliphatic; or heterocyclic polyvalent group and b has an average value of from 1 to 8.
  • the first epoxide disclosed herein above is at least one divinylarene oxide of the following structures:
  • each R 1 , R 2 , R 3 and R 4 is individually hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a oxidant-resistant group including for example a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl;
  • x is an integer of 0 to 4.
  • y is an integer greater than or equal to 2 with the proviso that x+y is an integer less than or equal to 6;
  • z is an integer of 0 to 6 with the proviso that z+y is an integer less than or equal to 8; and Ar is an arene fragment, preferably a 1,3-phenylene group.
  • the short chain polyalkylene glycol diglycidyl ether disclosed herein above is at least one or more of the formula
  • R 6 is H or Ci to C3 aliphatic group and d has an average value from 1 to 12, preferably the short chain polyalkylene glycol diglycidyl ether is poly (propylene glycol) diglycidyl ether having a molecular weight from 185 to 790.
  • the amine curing agent is at least one curing agent represented by the formula:
  • R 7 , Q, X, and Y at each occurrence are independently H, d to C14 aliphatic, C3 to C10 cycloaliphatic, or C6 to C14 aromatic or X and Y can link to form a cyclic structure;
  • Z is O, C, S, N, or P;
  • c is 1 to 8; and
  • p is 1 to 3 depending on the valence of Z.
  • the amine curing agent is represented by the formula
  • R at each occurrence is independently H or -CH 2 CH 2 NH 2 and h is 0 to 2 with the proviso that both h's cannot be 0.
  • the thermoset disclosed herein above further comprises (f) an acrylate monomer having an acrylate equivalent weight of 85 grams/equivalent to 160 grams/equivalent, wherein the acrylate monomer component is present in an amount from 1 to 12 part per hundred parts based on the total amount epoxy resin, preferably the acrylate component is hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, Methylene glycol diacrylate, 1,4- butanediol diacrylate, dipropylene glycol diacrylate, neopenyl glycol diacrylate, cyclohexane dimethanol diacrylate, pentaerythritol triacrylate, diptenaerythritol pentaacrylate, or combinations thereof.
  • an acrylate monomer having an acrylate equivalent weight of 85 grams/equivalent to 160 grams/equivalent wherein the acrylate monomer component is present in an amount from
  • Another embodiment of the present invention is a pipe at least partially encased by a thermal insulating layer wherein the insulating layer comprises the reaction product disclosed herein above.
  • thermoset materials can be used to thermally insulate any object for a surrounding fluid.
  • thermosets are suitable for insulation of substrates, such as oil pipelines in cold water and for insulating wellhead equipment.
  • the thermoset materials of the present invention may also be used for insulting manifolds, risers, field joints, configurations designated Christmas trees, jumpers, spool pieces and other related sub-sea architectures.
  • the thermoset materials may also be used to coat robotic parts, devices and vehicles used in sub-sea applications.
  • thermoset materials are prepared from by amine curing of (a) an ambient temperature liquid epoxy-terminated prepolymer, (b) a short chain polyalkylene glycol diglycidyl ether, (c) optionally a second epoxy, and (d) optionally a filler. While the thermosets are well suited for objects which are submerged in water, the thermosets may be used to coat objects which are not exposed to an aqueous environment.
  • thermoset resins are synthesized in at least two steps: first an epoxy-terminated prepolymer is formed and in the second step, the prepolymer, the short chain polyalkylene glycol diglycidyl ether, and optional a second epoxy, and/or filler are cured by an amine to form the final epoxy-based thermoset.
  • the prepolymer formed is a liquid at ambient conditions to promote flow especially when filling complex molds.
  • both the epoxy-terminated prepolymer and amine curing agent are liquid at ambient temperature.
  • the final thermoset contains "soft” structural segments, provided by the polyether.
  • the epoxy portion when reacted with suitable short polyfunctional amines, provides "hard” structural elements recurring along the ultimate thermoset polymer chain.
  • thermoset materials formed via the reaction of epoxides and amine curatives. Such thermosets are generally suitable for applications where thermosets with high flexibility and good hydrolysis resistance are needed.
  • the thermoset materials of the invention may be used generally in the areas of coatings, sealants, adhesives, gaskets, potting, jointing or casting.
  • the thermoset materials of the present invention may also be used in the automotive industry for engine mounts and suspension bushings.
  • such thermoset materials are prepared from amine curing a mixture of an epoxy resin containing an epoxy-terminated prepolymer, a short chain polyalkylene glycol diglycidyl ether, and optional a second epoxy, and/or filler.
  • the epoxy-based thermoset not including any filler, will generally display a percent elongation of greater than 5. In further embodiments the epoxy-based thermoset will have an elongation of at least 15, 20 or 25 percent.
  • the presence of the soft and hard segments provide for an epoxy-based thermoset having at least one Tg of less of less than 0°C.
  • Tg is used to mean the glass transition temperature and is measured via Dynamic Mechanical Thermal Analysis.
  • the epoxy-based thermoset will have at least one Tg of less than -15°C, -20°C, -30°C, or less than -40°C.
  • the epoxy-based thermoset will have at least one Tg of less than -0°C and at least one Tg of greater than 25 °C.
  • the epoxy based materials can generally be used in environments where the temperatures are up to about 180°C.
  • epoxy-based thermoset coatings of the present invention may be used for coating pipes or other sub-sea structures where the temperature of transported material may range up to 140°C, even up to 150°C, even up to 180°C.
  • the epoxy-based thermosets of the present invention without the addition of fillers, generally have a thermal conductivity of less than 0.18 W/m*K, as determined by ASTM C518.
  • the thermosets of the present invention have a thermal conductivity of less than 0.16 W/m*K.
  • the thermal conductivity may be further reduced with the addition of hollow spheres, such as glass bubbles.
  • an epoxy-based thermoset would display the toughness needed for various applications, have good hydrolytic stability, display a good cure profile, and have good insulation properties (low thermal conductivity). For instance, it was unexpected that an epoxy- based thermoset could display tensile strength in excess of 12 MPa, while displaying a maximum elongation of greater than 20%.
  • the epoxy-terminated prepolymer is formed by the reaction of a polyoxyalkyleneamine with a first epoxide or epoxy resin.
  • the polyoxyalkyleneamine may also be referred to as an amine terminated polyether.
  • the polyoxyalkyleneamine will have an average molecular weight of at least 3,000.
  • the polyoxyalkyleneamine will have an average molecular weight of less than 20,000. In a further embodiment the
  • polyoxyalkyleneamine will have a molecular weight of at least 3,500.
  • the polyether polyols for producing the polyoxyalkyleneamine are generally obtained by addition of a C 2 to Cs alkylene oxide to an initiator having a nominal functionality of 2 to 6, that is, having 2 to 6 active hydrogen atoms.
  • the alkylene oxide will contain 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. When two or more oxides are used, they may be present as random mixtures or as blocks of one or the other polyether.
  • the polyether polyol will be liquid at room temperatures.
  • the ethylene oxide content of the polyether polyol will be less than 30, less than 25, less than 20 or less than 15 weight percent ethylene oxide.
  • the polyether polyol is a poly(oxypropylene) polyol.
  • Catalysis for polymerization of alkylene oxide to an initiator can be either anionic or cationic.
  • Commonly used catalysts for polymerization of alkylene oxides include KOH, CsOH, boron trifluoride, a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate, or quaternary phosphazenium compound.
  • DMC double cyanide complex
  • initiators examples include glycerol, trimethylol propane, sucrose, sorbitol, pentaerythritol, ethylene diamine and aminoalcohols, such as, ethanolamine, diethanolamine, and triethanolamine.
  • the initiator for the polyether contains from 3 to 4 active hydrogen atoms.
  • the initiator is a polyhydric initiator.
  • the polyols will have an equivalent weight of at least about 500 and preferably at least about 750 up to about 1,500 or up to about 2,000.
  • polyether polyols having a molecular weight of 4,000 and above, based on trihydric initiators are used.
  • the conversion of the polyether to a polyoxyalkyleneamine can be done by methods known in the art. For example by reductive amination, as described, for example in USP 3,654,370, the contents of which are incorporated by reference.
  • R is the nucleus of an oxyalkylation-susceptible initiator containing 2-12 carbon atoms and 2 to 8 active hydrogen groups
  • U is an alkyl group containing 1-4 carbon atoms
  • T and V are independently hydrogen or U
  • n is number selected to provide a polyol having a molecular weight of as described above and m is an integer of 2 to 8 corresponding to the number of active hydrogen groups originally present in the initiator.
  • n will have a value of 35 to 100.
  • R has 2 to 6 or 2 to 4 active hydrogen groups.
  • the active hydrogen groups are hydroxyl groups.
  • R is an aliphatic polyhydric initiator.
  • R has 3 active hydrogen groups.
  • n will be less than 90, less than 80, less than 75, or less than 65.
  • U, T and V are each methyl.
  • the polyoxyalkyleneamine will generally have an amine equivalent weight of from about 900 to about 4,000. In a further embodiment the amine equivalent weight will be less than 3,000.
  • a single molecular weight polyoxyalkyleneamine may be used.
  • mixtures of different polyoxyalkyleneamines such as mixtures of tri- and higher functional materials and/or different molecular weight or different chemical composition materials, may be used.
  • Suitable polyoxyalkyleneamines commercially available are, for example;
  • JEFF AMINETM D4000 and JEFF AMINE T5000 form Huntsman Corporation.
  • the first epoxide or epoxy resins used in producing the epoxy terminated prepolymers (a) are compounds containing at least one vicinal epoxy group.
  • the epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted.
  • the epoxy resin may also be monomeric or polymeric.
  • the epoxy resin component is a polyepoxide.
  • Polyepoxide as used herein refers to a compound or mixture of compounds wherein at least one of the compounds contains more than one epoxy moiety.
  • Polyepoxide as used herein also includes advanced or partially advanced epoxy resins, that is, the reaction of a polyepoxide and a chain extender, wherein the resulting epoxy reaction product has, on average, more than one unreacted epoxide unit per molecule.
  • the epoxy resin component may be a solid or liquid at ambient temperature (10°C and above).
  • a "solid epoxy resin” or "SER” is an epoxy-functional resin that has a Tg generally greater than about 30°C. While the epoxy resin may be a solid, the final epoxy terminated prepolymer will be a liquid at ambient temperature. For ease of handling, in one embodiment the epoxy resin is a liquid at ambient temperatures.
  • the epoxy resin may be represented by the formula wherein R 5 is C 6 to Ci 3 ⁇ 4 substituted or unsubstituted aromatic, a Ci to C M , preferably Ci to C 8 alphatic, or cycloaliphatic; or heterocyclic polyvalent group and b has an average value of from 1 to 8, preferably from 1 to 4.
  • Aliphatic poly epoxides may be prepared from the known reaction of epihalohydrins and polyglycols.
  • Examples of aliphatic epoxides include trimethylpropane epoxide and diglycidyl- 1,2-cyclohexane dicarboxylate.
  • epoxies which can be employed herein include, epoxy resins such as, for example, the glycidyl ethers of polyhydric phenols or epoxy resins prepared from an epihalohydrin and a phenol or phenol type compound.
  • the phenol type compound includes compounds having an average of more than one aromatic hydroxyl group per molecule.
  • phenol type compounds include dihydroxy phenols, biphenols, bisphenols, halogenated biphenols, halogenated bisphenols, hydrogenated bisphenols, alkylated biphenols, alkylated bisphenols, trisphenols, phenol-aldehyde resins, novolac resins (i.e.
  • Examples of bisphenol A based epoxy resins useful in the present invention include commercially available resins such as D.E.R.TM 300 series and D.E.R. 600 series, commercially available from The Dow Chemical Company.
  • Examples of epoxy novolac resins useful in the present invention include commercially available resins such as D.E.N.TM 400 series, commercially available from The Dow Chemical Company.
  • the epoxy resin compounds may be a resin from an epihalohydrin and resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (l,l-bis(4-hydroxyphenyl)-l -phenyl ethane), bisphenol F, bisphenol K, bisphenol S, tetrabromobisphenol A, phenol-formaldehyde novolac resins, alkyl substituted phenol- formaldehyde resins, phenol- hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins, dicyclopentadiene-substituted phenol resins,
  • the epoxy resin includes those resins produced from an epihalohydrin and an amine. Suitable amines include diaminodiphenylmethane, aminophenol, xylene diamine, anilines, and the like, or combinations thereof.
  • Suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydro- and/or hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, isophthalic acid, methylhexahydrophthalic acid, and the like or combinations thereof.
  • cycloaliphatic epoxide consists of a saturated carbon ring having an epoxy oxygen bonded to two vicinal atoms in the carbon ring for example as illustrated by the following general formula:
  • R 5 and b are as defined above.
  • the cycloaliphatic epoxide may be a monoepoxide, a diepoxide, a polyepoxide, or a mixture of those.
  • any of the cycloaliphatic epoxide described in USP 3,686,359, incorporated herein by reference, may be used in the present invention.
  • the cycloaliphatic epoxides that may be used in the present invention include, for example, (3,4- epoxycyclohexyl-methyl)-3 ,4-epoxy-cyclohexane carboxylate, bis-(3 ,4-epoxycyclohexyl) adipate, vinylcyclohexene monoxide and mixtures thereof.
  • Another class of epoxy resins useful in the present invention are based on divinylarene oxide product illustrated gener s I -IV as follows:
  • each R 1 , R 2 , R 3 and R 4 individually may be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a oxidant-resistant group including for example a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; and z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.
  • the alkyl moiety will have from 1 to 36 carbon atoms. In further embodiments the alkyl will have less than 24, or less than 18 carbon atoms. In further embodiments the alkyl will have from 1 to 8 or from 1 to 6 carbon atoms. Similarly the cycloalkyl will contain from 5 to 36 carbon atoms. Generally the cycloalkyl will contain from 5 to 24 carbon atoms.
  • the aryl moiety present in the divinylarene dioxide will generally contain 12 carbon atoms or less.
  • An aralkyl group will generally contain 6 to 20 carbon atoms.
  • the divinylarene dioxide product produced by the process of the present invention may include for example alkyl-vinyl-arene monoxides depending on the presence of alkylvinylarene in the starting material.
  • the divinylarene dioxide produced by the process of the present invention may include for example divinylbenzene dioxide,
  • divinylnaphthalene dioxide divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof.
  • the epoxy resin may also contain a halogenated or halogen-containing epoxy resin compound.
  • Halogen-containing epoxy resins are compounds containing at least one vicinal epoxy group and at least one halogen.
  • the halogen can be, for example, chlorine or bromine, and is preferably bromine.
  • Examples of halogen-containing epoxy resins useful in the present invention include diglycidyl ether of tetrabromobisphenol A and derivatives thereof.
  • Examples of the epoxy resin useful in the present invention include commercially available resins such as D.E.R. 500 series, commercially available from The Dow Chemical Company.
  • the epoxy resin has a number average molecular weight of less than 20,000, preferably less than 10,000, and more preferably less than 8,000.
  • the epoxy resins useful in the present invention have an average molecular weight of from about 200 to about 10,000, preferably from about 200 to about 5,000, and more preferably from about 200 to about 1,000.
  • the epoxide equivalent weight of the epoxy resins is generally from about 100 to about
  • EW epoxide equivalent weight
  • the diepoxides useful in the present invention are the epoxy resins having an epoxy equivalent weight of from about 100 to about 500.
  • the relative amount of epoxy resin employed to make the prepolymer can be varied over wide ranges. Generally the epoxy resin used should be at present in a ratio of at least 3 epoxy groups per amino hydrogen atoms to avoid prepolymer gelling. In further embodiments the ratio of oxirane moieties per amine hydrogen is at least 5, at least 10 and generally up to 20 to 1.
  • the prepolymer is formed by reacting at least 4 moles of polyepoxide resin per mole of diamine at temperatures in the range of about 80°C for at least 1 hour with constant stirring. Exact temperatures and duration depend on the reactivity of the polyepoxide resins being utilized. The conditions for reaction of the epoxy resin with the polyoxyalkyleneamine are well known in the art.
  • the reaction when using a polyoxyalkyleneamine and epoxy resin which a liquid at ambient temperatures, no solvent is needed.
  • the mixture of polyoxyalkyleneamine and epoxy resin is heated to between 70 to 150°C for sufficient time to react the reactive hydrogen atoms available.
  • the reaction may be carried out in the presence of conventional catalysts that promote the reaction between amines and epoxides.
  • the reaction may be carried out in the presence of solvents suitable for dissolving the amine and/or epoxy.
  • the final epoxy-terminated prepolymer will be a liquid at ambient temperature, that is, generally a liquid at 25 °C and above. In a further embodiment, the epoxy- terminated prepolymer will be a liquid at 20°C and above. In another embodiment the epoxy- terminated prepolymer will be a liquid at 15°C and above. By liquid, it is inferred that the material is pourable or pumpable.
  • the liquid epoxy-terminated prepolymer (a) is present in the reaction mixture in an amount of equal to or greater than 40 weight percent, preferably equal to or greater than 45 weight percent, and more preferably equal to or greater than 50 weight percent based on the total weight of components (a), (b), and (c), if present.
  • the liquid epoxy-terminated prepolymer (a) is present in the reaction mixture in an amount of equal to or less than 99 weight percent, preferably equal to or less than 95 weight percent, and more preferably equal to or less than 90 weight percent based on the total weight of the components (a), (b), and (c), if present.
  • the amine curing agent is a monoamine or a polyamine having an equivalent weight of less than 200 and having 2 to 5 active hydrogen atoms. Generally the amine curing agent will have an equivalent weight of at least 20.
  • the amino equivalent weight means the molecular weight of the curing agent divided by the number of amine active hydrogen atoms. In a further embodiment, the amine or polyamine has from 2 to 4 active hydrogen atoms. In yet another embodiment, the amine curing agent has 4 amino active hydrogen atoms.
  • the amine curing agent is generally added to provide 0.8 to 1.5 amine equivalents (NH) per epoxy reactive group. In a further embodiment the ratio is from 0.9 to 1.1.
  • Suitable amine curing agents for use in the present invention include those represented by the following formula:
  • R 7 , Q, X, and Y at each occurrence are independently H, d toCw aliphatic, C3 to C 10 cycloaliphatic, or C6 to C14 aromatic or X and Y can link to form a cyclic structure;
  • Z is O, C, S, N, or P
  • c 1 to 8;
  • p 1 to 3 depending on the valence of Z.
  • Z is oxygen. In a further embodiment Z is oxygen and R 7 is hydrogen. In another embodiment X and Y are both hydrogen.
  • Cyclic diamines as represented by the following formula, may also be used curing agents in the present invention:
  • R at each occurrence is independently H or -CH 2 CH 2 NH 2 and h is 0 to 2 with the proviso that both h's cannot be 0.
  • Aromatic amine curing agents may also be used such as toluene -2,4-diamine; toluene- 2,6-diamine, isomers of phenylene diamine; aniline; and the like.
  • the amine curing agent can be the steric and geometric isomers of isophorone diamine, bis(aminomethyl) cyclohexane, methylcyclohexane diamine, or cyclohexane diamine.
  • Examples of specific amine-terminated curing agents include: monoethanolamine; 1- amino-2-propanol; l-amino-3-propanol; l-amino-2-butanol; 2-amino-l-butanol; isophorone diamine; methylcyclohexane diamine; l,3-bis(aminomethyl) cyclohexane; piperazine;
  • amine curing agent is an isophorone diamine. In yet another embodiment the amine curing agent is combination of isophorone diamine and aminoethylpiperazine.
  • amine terminated polyethers having an equivalent weight of less than 200 such as JEFF AMINE D400 from Huntsman Chemical Company.
  • the curing may contain a combination of an aliphatic and an aromatic curing agent to have a staged curing process.
  • the combination of amine curing agents allows a first curing step, generally done at 70°C to 80°C whereby the aliphatic amine reacts with the epoxy moiety to form a prepreg, and a second curing step done at temperatures above 80°C for curing with the aromatic amine.
  • Component (b) a short chain polyalkylene glycol diglycidyl ether, is added with the prepolymer in the second step.
  • Preferred short chain polyalkylene glycol diglycidyl ethers for use in the reaction mixture of the present invention are represented by the following formula:
  • R 6 is H or Ci to C3 aliphatic group and d has an average value from 1 to 12.
  • Suitable short chain polyalkylene glycol diglycidyl ethers include diglycidyl ether of poly (butylene glycol), glycidyl ethers of poly (propylene glycol) or glycidyl ethers of poly (ethylene glycol), preferably the short chain polyalkylene glycol diglycidyl ether is poly (propylene glycol) diglycidyl ether.
  • the short chain polyalkylene glycol diglycidyl ether has molecular weight from 185 to 790. More preferably, the short chain polyalkylene glycol diglycidal ether has molecular weight from 350 to 650.
  • the ratio of the molecular weight of the polyoxyalkyleneamine to the molecular weight of the polyalkylene glycol diglycidal ether is in the range of 6 to 12, more preferably in the range of 8 to 10.
  • the short chain polyalkylene glycol diglycidyl ether is poly (propylene glycol) having molecular weight from 185 to 790. In a further embodiment of the present invention, the poly (propylene glycol) has a molecular weight from 350 to 650.
  • the short chain polyalkylene glycol diglycidyl ether (b) is added in an amount of equal to or greater than 1 weight percent, preferably equal to or greater than 5 weight percent, and more preferably equal to or greater than 10 weight percent based on the total weight of components (a), (b), and (c), if present.
  • the short chain polyalkylene glycol diglycidyl ether (b) is added in an amount of equal to or less than 40 weight percent, preferably equal to or less than 30 weight percent, and more preferably equal to or less than 20 weight percent based on the total weight of components (a), (b), and (c), if present.
  • the second epoxide (c), if added, is added in an amount of equal to or greater than 1 weight percent, preferably equal to or greater than 5 weight percent, and more preferably equal to or greater than 10 weight percent based on the total weight of components (a), (b), and (c), if present.
  • the second epoxide (c) is added in an amount of equal to or less than 45 weight percent, preferably equal to or less than 35 weight percent, and more preferably equal to or less than 25 weight percent based on the total weight of components (a), (b), and (c), if present.
  • thermosets of the present invention include catalysts, flame retarding agents, plasticizers, antioxidants, UV stabilizers, adhesion promoters, dyes, pigments, reinforcing agents, and fillers (d) such as wollastonite, barites, mica, feldspar, talc, silica, crystalline silica, fused silica, fumed silica, glass, metal powders, carbon nanotubes, graphene, calcium carbonate, or glass beads.
  • fillers such as wollastonite, barites, mica, feldspar, talc, silica, crystalline silica, fused silica, fumed silica, glass, metal powders, carbon nanotubes, graphene, calcium carbonate, or glass beads.
  • the other additive(s), for example a filler (d), if present is added in an amount of equal to or greater than 1 part by weight, preferably equal to or greater than 5 parts by weight, and more preferably equal to or greater than 10 parts by weight wherein parts are based on 100 parts of components (a), (b), and (c), if present.
  • the other additive(s), for example a filler (d), if present is added in an amount of equal to or less than 40 parts by weight, preferably equal to or less than 30 parts by weight, and more preferably equal to or less than 20 parts by weight wherein parts are based on 100 parts of components (a), (b), and (c), if present.
  • one or more acrylate monomer (f) may be added with the prepolymer in the second step.
  • the acrylate has an acrylate equivalent weight of 85 grams/equivalent to 160 grams/equivalent.
  • Acrylate equivalent weight may be calculated by dividing the molecular weight of the acrylate component by the number of acrylate moieties present in the acrylate component.
  • the acrylate component is limited exclusively to polyfunctional acrylates, e.g., compounds having two or more vinyl groups.
  • the polyfunctional acrylate is selected from the group consisting of hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, Methylene glycol diacrylate, 1,4-butanediol diacrylate, dipropylene glycol diacrylate, neopenyl glycol diacrylate, cyclohexane dimethanol diacrylate, pentaerythritol triacrylate, diptenaerythritol pentaacrylate and combinations thereof.
  • Acrylate equivalent weight of these polyfunctional acrylates is: 113 grams/equivalent (hexanediol diacrylate), 150 grams/equivalent (tripropylene glycol diacrylate), 107 grams/equivalent (diethylene glycol diacrylate), 99 grams/equivalent (trimethylolpropane triacrylate), 129 grams/equivalent (Methylene glycol diacrylate), 99 grams/equivalent (1,4-butanediol diacrylate), 121 grams/equivalent (dipropylene glycol diacrylate), 106 grams/equivalent (neopenyl glycol diacrylate), 126 grams/equivalent (cyclohexane dimethanol diacrylate), 99 grams/equivalent (pentaerythritol triacrylate), and 105 grams/equivalent (diptenaerythritol pentaacrylate).
  • the acrylate monomer is present in an amount equal to or greater than 0.1 part per hundred (pph), preferably equal to or greater than 1 pph, and more preferably equal to or greater than 5 pph based on the total amount of epoxide in the reaction mixture.
  • pph 0.1 part per hundred
  • the acrylate monomer is present in an amount equal to or less 30 pph, preferably equal to or less than 20 pph, more preferably equal to or less than 15 pph, even more preferably equal to or less than 12 pph based on the total amount of epoxide in the reaction mixture.
  • a process for providing an epoxy based material coating on a surface comprises the steps of
  • the epoxy based material can be applied as one or more layers to a surface by known methods in the art, such as spraying, brush coating, extrusion, immersion or flooding or by means of rollers or doctor applicators.
  • the epoxy based material is suitable for formation of coating on essentially any surface, such as metals, plastics, wood, concrete, asphalt or glass.
  • the epoxy based materials of the present invention may be used in conjunction with other layers, such as an anticorrosion layer or adhesion promoting layer.
  • the thermosets of the present invention may also comprise at least one layer of a multi-layered composite or coating.
  • the epoxy based materials may be combined with one or more additional layer of material, such as a paint, a silicone, a polyurethane, an epoxy, a polyolefin, or combinations thereof.
  • the coating provided may have a thickness in the range up to 10 mm, typically in the range of 0.1 to 10 mm. In a further embodiment the coating will have a density of more than 0.5 g/cm 3 .
  • the epoxy based material may also be used in cast molding for the production of molded article such as wheels or automotive parts. In production of such materials, the epoxy terminated prepolymer, the short chain polyalkylene glycol diglycidyl ether, optional second epoxide and/or filler, the curing agent, and any additional additives are introduced into a mold, the mold is closed and the reaction mixture is allowed to cure. In such applications, the mold is generally heated to between 80°C and 120°C.
  • the thermal conductivity of the epoxy material can be decreased by the addition of fillers.
  • suitable fillers include glass hollow spheres, hollow thermoplastic spheres composed of acrylic type resins such as polymethyl methacrylate, acrylic modified styrene, polyvinylidene chloride or copolymer of styrene and methyl methacrylate; phenolic resins; silica, ceramic or carbon spheres.
  • Preferred fillers are hollow microspheres.
  • the term "hollow" with respect to the hollow objects for use in the present invention is to be understood as at least 50% of the enclosed volume being filled with gaseous fluid. Optionally, the enclosed volume being only filled with gaseous fluid.
  • Such filled systems are generally referred to as syntactic materials.
  • hollow glass microspheres examples include, for example, SCOTCHLITETM
  • GLASSBUBBLESTM from 3M hollow polymer microspheres, for example EXPANCELTM from Akzo Noble, or hollow ceramic microspheres, for example CENOSPHERESTM from Sphere Services Inc.
  • hollow microspheres provide less than 35 wt%, or less than 25wt%, of the syntactic coating.
  • hollow glass beads provide 5 to 15 wt% of the syntactic coating, the percentage by weight (wt%) being relative to the whole formulation.
  • microspheres are blended with the epoxy-terminated prepolymer by techniques known in the art.
  • viscosity modifying agents known in the art may be added.
  • examples of such additives include diglycidyl ether of butane diol, glycidyl ethers of fatty acid or natural oils or TEP (triethyl phosphate, (C 2 H 5 ) 3 P0 4 ).
  • other additives which may be used with the thermosets of the present invention include catalysts, flame retarding agents, plasticizers, antioxidants, UV stabilizers, adhesion promoters, dyes, pigments, fillers other than glass bubbles, and reinforcing agents.
  • the epoxy-based thermoset material of the present invention may be used in the insulation of any object from a surrounding fluid.
  • the thermoset materials are used for insulating oil and gas flowlines, manifolds, risers, field joints, configurations designated Christmas trees, jumpers, spool pieces and other related sub-sea architecture.
  • the pipe that is coated with the thermoset material can have any outer diameter, inner diameter and length. Generally the outer diameter is at least 10 cm and the length of 1 meter or more.
  • Subsea Christmas tree structures are well known in the industry and as described, for example, in USP 6,520,261 and 6,746,761 ; the portions of such documents disclosing such structures being incorporated herein by reference.
  • such structures will include a production bore in communication with the well bore, a production outlet connected to the production bore a flow loop in communication with the production outlet.
  • the structures may include other typical components such as one or more production valves for controlling flow through the production outlet.
  • the insulation material is applied to those portions of the Christmas tree which are most exposed to the surrounding seawater and through which the produced fluids will flow.
  • a process for providing an epoxy based material coating for offshore applications comprises the steps of: providing a surface to be coated; providing an epoxy terminated prepolymer; providing a short chain polyalkylene glycol diglycidyl ether, optionally providing a second epoxy, optionally providing a filler; providing an amine terminated curing agent; bringing the epoxy terminate prepolymer, amine terminated curing agent, short chain polyalkylene glycol diglycidyl ether, and optional second epoxy and/or filler, into contact with said surface; and reacting said epoxy terminated prepolymer, short chain polyalkylene glycol diglycidyl ether, optional second epoxy and/or filler, and amine terminated curing agent thereby providing an epoxy based coating.
  • reaction mixture to the surface to be coated is carried out by methods known in the art. Examples are rotation casting, casting in molds and the mixing pot process. See, for example, publications WO 02/072701 ; WO 2009/085191; and USP 6,955,778.
  • the epoxy-based thermoset material When the epoxy-based thermoset material is applied to a complex structures, such a Christmas tree using a variety of methods known in the art for application may be used.
  • a form or mold is constructed around the object to be insulated.
  • the epoxy-terminated prepolymer/short chain polyalkylene glycol diglycidyl ether/amine curing agent/optional additive(s) are thoroughly mixed and then cast between the object and the mold and allowed to cure. Once the material has cured, the mold is removed.
  • the insulation material can be pre-cast into sections which are shaped to complement the object to be insulated. Once the pre-cast sections have cured, they may be secured to the object using adhesives, mechanical fasteners, or any other suitable means.
  • the insulation material can also be sprayed on the object.
  • the mixture is poured by means of a film nozzle onto a pipe which is rotating about its axis and the desired coating thickness is set via the speed at which the nozzle is advanced.
  • a pretreated section of pipe is laid in a heated mold, which generally has been treated with mold release agents, the mold is closed, inclined and filled from the lowest point via a hose until the reacting mixture comes out of the mold at the highest point.
  • the mold is generally heated to between 80°C and 120 °C.
  • a reacting system metering machine is introduced into a mixing pot which is open at the bottom.
  • a defined amount of hollow microspheres is metered in by means of a screw metering device.
  • the reaction mixture can be applied to a rotating pipe or introduced into a mold via an outlet orifice.
  • the coating provided may have a thickness in the range up to 100 mm, typically in the range of 10 to 50 mm. In a further embodiment the coating will have a density of more than 0.5 g/cm 3 .
  • the vessel is degassed, padded with nitrogen and the temperature slowly increased to 125 °C via a heated jacket. The internal temperature is maintained at 120°C and held for three hours.
  • the vessel is then cooled to 80°C, the agitator stopped and the sample discharged.
  • the epoxy terminated prepolymer is found to be a viscous liquid at 25 °C (approximately 90,000 cPs) with a measurable epoxy equivalent weight of 412 g/mol (463 actual). Examples 2 and 3. Thermoset Polymer Preparation
  • the epoxy terminated prepolymer prepared in Example 1 additional amount of the D.E.R. 736, which is a polyalkyleneglycol diglycidylether available from The Dow Chemical Company and DE 383 epoxy resin are added to lidded cups suitable for use in a FLACKTEK SPEEDMIXERTM and the sample mixed for 15 seconds at 800 rpm, then mixed at 2350 rpm for 2 minute and then heated in a 50°C oven. Then amine curing agent is added according to the formulations in the Table 1 , the values are in parts by weight. Either isophorone diamine available from Evoniks as Versamid IPDA is used.
  • D.E.R. 736 which is a polyalkyleneglycol diglycidylether available from The Dow Chemical Company and DE 383 epoxy resin are added to lidded cups suitable for use in a FLACKTEK SPEEDMIXERTM and the sample mixed for 15 seconds at 800 rpm, then mixed at 2350 rpm for 2 minute and then heated
  • the samples are mixed on a FLACKTEK SPEEDMIXER for 15 seconds at 800 rpm followed by 2350 rpm for 2 minute.
  • the mixtures are then poured into closed aluminum molds that are preheated to 50°C.
  • the molds are placed back into the oven and allowed to cure for approximately 12 hours at 120°C, demolded, and cooled to room temperature for 24 hours.
  • Tensile properties are then measured according to ASTM D412 and thermal properties are measured via Dynamic Mechanical Thermal Analysis on either TA Instruments ARES G2 or ARES instruments. Frequency of 1 Hz and a heating rate 5°C/min is used to heat the samples from -100°C to 180°C and this cycle is repeated twice.
  • the measured properties of the produced polymers are given in Table 2.
  • the epoxy terminated prepolymer prepared in Example 1 additional amount of the D.E.R. 736 and resorcinol diglycidylether, which is an epoxy resin available from CVC Thermoset Specialties as ERISYSTM RDGE are added to lidded cups suitable for use in a FLACKTEK SPEEDMIXER and the sample mixed for 15 seconds at 800 rpm, then mixed at 2350 rpm for 2 minute and then heated in a 50°C oven. Then l,3-bis(aminomethyl) cyclohexane, an amine curing agent available from Mitsubishi Gas Chemical Company is added according to the formulations shown in the Table 3, the values are in parts by weight.
  • the epoxy terminated prepolymer prepared in Example 1 additional amount of the polyalkyleneglycol diglycidylether, D.E.R. 736, D.E.R. 383 epoxy resin, and a diacrylate monomer are added to gallon pails suitable for use in a STATEMIX mixer and the sample mixed for 2 minutes at 1000 rpm and then allowed to cool down. Then amine curative agent(s) are added according to the formulations shown in the Table 5, the values are in parts by weight. Aminoethylpiperazine is available from The Dow Chemical Company and 1 ,6-hexanediol diacrylate and trimethylolpropane triacrylate is available from Sartomer Americas as SR238 and SR351.
  • the samples are mixed on the STATEMIX mixer for 2 minutes at 1000 rpm.
  • the mixtures are then poured into an open stainless steel container of 7 inch diameter, such that the height of the resin in the container is approximately 4 inches.
  • a thermometer is held in place such that its sensing junction is approximately at the center of the resin, measuring the core temperature.
  • An additional thermometer is placed outside the container at approximately 2 inch height from the bottom, measuring the wall temperature. Temperatures at these locations are continuously recorded. The maximum temperature recorded and the time interval at which it occurred measured from the time when the mixing of the resin and the curative agent is initiated are given in Table 6.
  • Example 6 reduces the maximum exotherm temperature achieved when compared to Example 9 where no acrylate monomer is used.
  • use of the difunctional acrylate 1,6-hexanediol diacrylate (HDD A) increases the time taken achieve the maximum temperature whereas the use of the trifunctional acrylate reduces the time taken to achieve maximum temperature.
  • the moldings of Examples 6 to 8 (containing an acrylate monomer) show no surface defects such as wilting and fingering, which are otherwise evident in moldings prepared from Examples 2 and 9 (not containing an acrylate monomer).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
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  • Epoxy Resins (AREA)

Abstract

L'invention concerne un matériau isolant comprenant une composition thermodurcie. Ces composés thermodurcis sont le produit de réaction d'un prépolymère terminé par un époxy liquide à température ambiante, d'un éther diglycidylique de polyalkylène glycol à chaîne courte, éventuellement d'un second époxy et/ou d'une charge, et d'un agent de durcissement comprenant au moins une amine ou une polyamine. Ledit produit de réaction donne un composé thermodurci qui a une aptitude au traitement et une flexibilité comparables à celles du polyuréthane avec une bonne stabilité thermique et hydrolytique et une ténacité et une résistance améliorées. Le matériau isolant est particulièrement utile en tant qu'isolant thermique et revêtement pour des applications relatives au gaz et au pétrole sous-marin.
PCT/US2016/044030 2015-08-07 2016-07-26 Matériaux époxy et leur utilisation dans des applications sous-marines WO2017027199A1 (fr)

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