WO2017027201A1 - Matériaux époxy présentant une aptitude au traitement améliorée et leur utilisation - Google Patents

Matériaux époxy présentant une aptitude au traitement améliorée et leur utilisation Download PDF

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Publication number
WO2017027201A1
WO2017027201A1 PCT/US2016/044032 US2016044032W WO2017027201A1 WO 2017027201 A1 WO2017027201 A1 WO 2017027201A1 US 2016044032 W US2016044032 W US 2016044032W WO 2017027201 A1 WO2017027201 A1 WO 2017027201A1
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Prior art keywords
thermoset
epoxy
epoxide
weight
equivalent
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PCT/US2016/044032
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English (en)
Inventor
Rujul M. MEHTA
Mark W. Brown
Pankaj Gupta
Dwight D. Latham
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Dow Global Technologies Llc
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Publication of WO2017027201A1 publication Critical patent/WO2017027201A1/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
    • C08G59/226—Mixtures of 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
    • C08G59/40—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

Definitions

  • thermosets for applications such as sealants, adhesives, coatings, gaskets, jointing and castings.
  • thermoset polymers include epoxies, polyurethanes, two-part silicones, and vulcanized rubber; each of these thermosets has positive and negative attributes.
  • Epoxies are usually rigid polymers that are formed from the reaction of an epoxy resin and curative agent such as an amine, or polyamine or an anhydride and are preferred for their superior mechanical properties and resistance to high temperature and or chemically aggressive environments. Epoxies generally exhibit limited flexibility and extension.
  • Polyurethanes are formed from the reaction of a polyol and isocyanate and are preferred for the ease of processing, wide range of mechanical properties spanning from rigid polymers to elastomers that can be obtained depending on the components chosen, and good adhesive properties to a range of substrates. Polyurethanes are generally limited in their thermal and hydrolytic stability.
  • Two-part cast silicone elastomers and vulcanized rubbers typically have thermal and hydrolytic stabilities that exceed polyurethanes, however; their application is generally limited to softer systems, equal to or less than 80 Shore A, that normally require long cure and demold times, e.g., 15 hours or more.
  • Vulcanized rubbers also require high temperature molding processes that limit their use in field applications, form fitting, or assembly applications without the use of additional primers and adhesives for bonding.
  • Silicones can be cast at ambient temperatures but suffer the same deficiencies as vulcanized rubbers in terms of adhesion and are generally more expensive than urethane systems.
  • thermosets which have polyurethane like processing and flexibility with good thermal and hydrolytic stability, toughness, strength, and improved processability.
  • This invention provides an amine cured epoxy 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 comprises the reaction product of (a) from 50 to 99 weight percent of an ambient temperature liquid epoxy-terminated prepolymer formed by reacting a polyoxyalkyleneamine having a molecular weight of from 3,000 to 20,000 with an excess of epoxide, wherein the polyoxyalkyleneamine is represented by the formula
  • 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 Cis substituted or unsubstituted aromatic, a Ci to Cs 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 C6 to Cis substituted or unsubstituted aromatic, a Ci 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 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;
  • 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 is H or d 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, Ci to C14 aliphatic, C3 to Cio 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 8 -N N— R 8 wherein R 8 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.
  • Another embodiment of the present invention is a multi-layered composite or coating comprising at least one layer comprising the thermoset disclosed herein above, preferably the multilayer coating further comprising one or more layer comprising a paint, a silicone, a polyurethane, an epoxy, a polyolefin, or combinations thereof.
  • FIG. 1 is a photograph of an example of a molded, cured thermoset composition of the present invention.
  • FIG.2 is a photograph of a molded, cured thermoset composition that is not an example of the present invention.
  • 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. In particular, such thermoset materials are prepared from amine curing of epoxy resins containing an epoxy-terminated prepolymer.
  • thermoset resins are synthesized as follows: in a first step, an epoxy- terminated prepolymer (a) is formed and in a second step, the prepolymer formed in the first step is combined with one or more acrylate monomer and the mixture is 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 network.
  • 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.
  • 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, have good insulation properties (low thermal conductivity), and have improved processability. 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 polyoxyalkyleneamme with a first epoxide or epoxy resin.
  • the polyoxyalkyleneamine may also be referred to as an amine terminated polyether.
  • polyoxyalkyleneamine will have an average molecular weight of at least 3,000. Generally 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. In one
  • polyether polyol is a poly(oxypropylene) polyol.
  • Catalysis for polymerization of alkylene oxide to an initiator can be either anionic or cationic.
  • catalysts for polymerization of alkylene oxides include KOH, CsOH, boron trifluoride, a double cyanide complex (DMC) catalyst such as zinc
  • 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 polyoxyaikyleneamine 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 polyoxyaikyleneamine 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 C6 to Cis substituted or unsubstituted aromatic, a Ci to C 14, preferably Ci to Cs alphatic, or cycloaliphatic; or heterocyclic polyvalent group and b has an average value of from 1 to 8, preferably from 1 to 4.
  • Aliphatic polyepoxides 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 hydro xyl 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, tetramethylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A, or combinations thereof.
  • the epoxy resin includes those resins produced from an epihalohydrin and an
  • 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 follo
  • R 5 and b are as defined above.
  • the cycloaliphatic epoxide may be a monoepoxide, a diepoxide, a polyepoxide, or a mixture of those.
  • 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 generally by general chemical Structures 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 8000 and more preferably from about 100 to about 4000.
  • 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. In one embodiment, the prepolymer is formed by reacting no less than 4 moles of polyepoxide resin per mole of diamine at temperatures in the range of about 80°C for not less than 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. Generally, when using a polyoxyalkyleneamine and epoxy resin which a liquid at ambient temperatures, no solvent is needed. To promote the reaction, 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 second step of making the epoxy based thermoset of the present invention consists of reacting a mixture consisting of the epoxy prepolymer (a) and the acrylate monomer having an acrylate equivalent weight of 85 grams/equivalent to 160 grams/equivalent (b) with an amine terminated curing agent.
  • the mixture that is reacted with an amine terminated curing agent has only the epoxy prepolymer (a) and the acrylic monomer (b) and no other components, i.e., no short chain polyalkylene glycol diglycidyl ether (c); no second epoxide (d), and no filler (e).
  • the second step of making the epoxy based thermoset of the present invention consists of reacting a mixture consisting of the epoxy prepolymer (a), the acrylate monomer having an acrylate equivalent weight of 85 grams/equivalent to 160 grams/equivalent (b), and a second epoxide (d) with an amine terminated curing agent.
  • the mixture that is reacted with an amine terminated curing agent has only the epoxy prepolymer (a), the acrylic monomer (b), and second epoxide (d) and no other components, i.e., no short chain polyalkylene glycol diglycidyl ether (c) and no filler (e).
  • 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, Ci toCw aliphatic, C3 to Cio 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; l-amino-2-propanol; l-amino-3-propanol; l-amino-2-butanol; 2-amino-l-butanol;
  • amine curing agent is an isophorone diamine.
  • 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), one or more acrylate monomer, is 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, triethylene glycol diacrylate, 1,4-butanediol diacrylate, dipropylene glycol diacrylate, neopenyl glycol diacrylate, cyclohexane dimethanol diacrylate, pentaerythritol triacrylate, dipentaerythritol 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 (triethylene 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 (dipentaerythritol pentaacrylate).
  • the acrylate monomer is present in an amount equal to or greater than 1 weight percent, preferably equal to or greater than 3 weight percent, and more preferably equal to or greater than 5 weight percent wherein weight percents are based on the total weight of components (a) and (b), and (c) and/or (d), if present.
  • the acrylate monomer is present in an amount equal to or less than 15 weight percent, preferably equal to or less than 12 weight percent, and more preferably equal to or less than 10 weight percent wherein weight percents are based on the total weight of components (a) and (b), and (c) and/or (d), if present.
  • Optional component (c) 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: wherein R 6 is H or d to C 3 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) and (b), and (c) and/or (d), if present. 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) and (b), and (c) and/or (d), if present.
  • Optional component (d), a second epoxide, 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) and (b), and (c) and/or (d), if present. If present, the second epoxide (d) 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) and (b), and (c) and/or (d), 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 (e), 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) and (b), and (c) and/or (d), if present.
  • the other additive(s), for example a filler (e), 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) and (b), and (c) and/or (d), if present.
  • 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.
  • the epoxy terminated prepolymer, acrylate monomer, optional short chain polyalkylene glycol diglycidyl ether and/or 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.
  • the mold is generally heated to between 80°C and 120°C.
  • conventional coatings may show a propensity to form cracks and disbondment from the object. Not to be held to any particular theory, we believe this behavior may be attributed to residual stresses in the coating, developed during shrinkage occurring during the casting process, stresses which exceed the mechanical strength of the thermoset. In some cases, disbondment failures manifest as cavities near the coating/object interface. This defect has can be attributed to the appearance of residual stresses in the coating, developed at the time the resin near the object wall has still not achieved its gel-point and the residual stress exceed the cohesive strength of the pre-gelled resin.
  • thermoset compositions comprising an acrylate monomer of the present invention demonstrate reduced shrinkage and/or cavitation when cast around an object such as a pipe.
  • 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).
  • 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 1 , 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 was initiated are given in Table 2.
  • Example 5 and Comparative Example C2 are removed from the stainless steel container and photographed, FIG. 1 and FIG. 2.
  • FIG. 1 the molding of Examples 5 (containing an acrylate monomer) does not show surface defects such as cavities or fingering.
  • FIG. 2 the molding of
  • Comparative Example C2 shows both cavities and fingering surface defects.

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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)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne des compositions thermodurcies. 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. Ces composés thermodurcis peuvent être utilisés dans des applications telles que des matériaux d'étanchéité, des adhésifs, des revêtements, des joints d'étanchéité, et des pièces d'assemblage et coulées.
PCT/US2016/044032 2015-08-13 2016-07-26 Matériaux époxy présentant une aptitude au traitement améliorée et leur utilisation WO2017027201A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4835241A (en) * 1987-06-29 1989-05-30 Texaco Inc. Epoxy coatings using acrylate esters, polyetherpolyamines and piperazine(s)
US5708058A (en) * 1995-09-29 1998-01-13 Vianova Resins Gmbh Aqueous coating composition based on low-solvent modified epoxy resin dispersions
US20080095946A1 (en) * 2004-11-22 2008-04-24 Hoefer Rainer Radiation Curable Compositions
WO2012030339A1 (fr) * 2010-09-01 2012-03-08 Dow Global Technologies Llc Matériaux d'isolation élastomères et l'utilisation de ceux-ci dans des applications sous-marines
WO2012030338A1 (fr) * 2010-09-01 2012-03-08 Dow Global Technologies Llc Matériaux époxy élastomères et l'utilisation de ceux-ci
WO2012148815A1 (fr) * 2011-04-26 2012-11-01 Dow Global Technologies Llc Compositions durcissables

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4835241A (en) * 1987-06-29 1989-05-30 Texaco Inc. Epoxy coatings using acrylate esters, polyetherpolyamines and piperazine(s)
US5708058A (en) * 1995-09-29 1998-01-13 Vianova Resins Gmbh Aqueous coating composition based on low-solvent modified epoxy resin dispersions
US20080095946A1 (en) * 2004-11-22 2008-04-24 Hoefer Rainer Radiation Curable Compositions
WO2012030339A1 (fr) * 2010-09-01 2012-03-08 Dow Global Technologies Llc Matériaux d'isolation élastomères et l'utilisation de ceux-ci dans des applications sous-marines
WO2012030338A1 (fr) * 2010-09-01 2012-03-08 Dow Global Technologies Llc Matériaux époxy élastomères et l'utilisation de ceux-ci
WO2012148815A1 (fr) * 2011-04-26 2012-11-01 Dow Global Technologies Llc Compositions durcissables

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