WO2023114041A1 - Résines de polyuréthane à groupes fonctionnels époxy et carbonate cyclique et leurs polymères thermodurcissables - Google Patents

Résines de polyuréthane à groupes fonctionnels époxy et carbonate cyclique et leurs polymères thermodurcissables Download PDF

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Publication number
WO2023114041A1
WO2023114041A1 PCT/US2022/051904 US2022051904W WO2023114041A1 WO 2023114041 A1 WO2023114041 A1 WO 2023114041A1 US 2022051904 W US2022051904 W US 2022051904W WO 2023114041 A1 WO2023114041 A1 WO 2023114041A1
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cyclic carbonate
diisocyanate
compound
dual
group
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PCT/US2022/051904
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English (en)
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Alan Ekin
Dean C. Webster
Jingbo Wu
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Covestro Llc
North Dakota State University
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Priority claimed from EP22154904.1A external-priority patent/EP4223825A1/fr
Application filed by Covestro Llc, North Dakota State University filed Critical Covestro Llc
Publication of WO2023114041A1 publication Critical patent/WO2023114041A1/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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic

Definitions

  • the present invention relates in general to polymers, and more specifically to dual-cure epoxy and cyclic carbonate-containing urethane compounds and their thermosetting polymers.
  • These dual-cure polymers contain at least one epoxy and at least one cyclic carbonate and; thus, can react with compounds that are reactive towards epoxies and towards cyclic carbonates.
  • High performance paint and coating systems are needed for many applications ranging from aircraft, ships, chemical plants, flooring, bridges, and many others. Although there are many coatings binder systems available, the two most prominent are epoxy coatings and polyurethane coatings.
  • Epoxy resin systems are often used as primers because they provide good adhesion to most substrates and provide a barrier for anticorrosion.
  • a typical epoxy system involves a bisphenol-A (BPA) based epoxy resin that is cured with a multifunctional amine curing agent.
  • BPA bisphenol-A
  • liquid BPA epoxy resins are used such as EPON 828 from Hexion or DER 331 from Olin Chemicals.
  • Amine curing agents can be simple compounds such as bis(p-amino cyclohexyl) methane (PACM), isophorone diamine (IPDA) or more complex amine compounds such as polyamide resins, polyamidoamine resins, polyphenalkamine resins, or epoxy resin adducts.
  • the pot-life is defined as the time for the viscosity to double, however; the pot life for any given coating system is that time where the viscosity is suitable for application. More information about epoxy resin technology can be found in various reference materials including B. Ellis, ed., Chemistry and Technology of Epoxy Resins, Springer Science, 1993; H. Panda, Epoxy Resins Technology Handbook, 2 nd Revised Edition, Asia Pacific Business Press, 2019; C.
  • Epoxy Resins Chemistry and Technology, 2 nd Edition, Routledge, 2018. [0004] In addition to amines, epoxy resins also react with themselves (homopolymerization), anhydrides, phenols, and/or thiols. An epoxy formulation may contain multiple different kinds of curing agents as well as the right conditions for homopolymerization.
  • Polyurethane coatings represent a class of high-performance systems that can be used for a number of different applications. Polyurethanes are highly desired for their durability, toughness, and abrasion resistance, which is believed to be a result of extensive hydrogen bonding.
  • Two component (2K) polyurethane coatings involve the reaction of a polyol with a polyisocyanate. As with epoxy resins, the curing reactions start as soon as the components are mixed; therefore, the coating system is supplied in two packages that are mixed just prior to application.
  • the polyol can be an acrylic polyol, a polyester polyol, a polyether polyol, a polyurethane polyol, or a polycarbonate polyol.
  • the polyisocyanate component can be based on aromatic or aliphatic building blocks. Aromatic polyisocyanates react very rapidly, while aliphatic polyisocyanates react slower; however, it is possible to accelerate the curing with the use of catalysts. Aliphatic polyisocyanates are preferred for use where the coating requires weathering performance. More information about polyurethanes and their use in coatings can be found in various reference materials including Szy cher’s Handbook of Polyurethanes, 2 nd edition, CRC Press, 2012; U. Meier-Westhues, Polyurethanes: Coatings, Adhesives and Sealants, Vincentz Network, 2007.
  • Glycidyl carbamate-functional resins are made by reacting isocyanate-functional resins with glycidol.
  • Glycidyl carbamates are typically synthesized by the reaction of a polyisocyanate with glycidol.
  • Pattison disclosed the synthesis of linear epoxy urethane compounds by the reaction of polytetramethylene ether glycol with an excess of toluene-2,4-diisocyanate (TDI), followed by reaction with glycidol. The product is mixed with a diamine and cured to form an elastomer.
  • Glycidyl carbamate- functional resins could be rendered water dispersible by partial replacement of glycidol with polyethylene glycol and cured using waterborne amine curing agents (J. Coat. Tech. Res., 6, 735-747 (2011); U.S. Pat. Nos. 7,776,956 and 9,676,895).
  • linear glycidyl carbamate resins can be made and cured with amines (J. Coat. Tech. Res., 10(2), 141-151 (2012)).
  • Hybrid sol-gel systems can also be synthesized by reactions with various silanes (Prog. Org. Coat., 66(1), 73-85 (2009); Prog. Org. Coat., 64(2-3) 128-137 (2009); Prog. Org. Coat., 63(4) 405-415 (2008); and U.S. Pat. No. 8,097,741).
  • glycidyl carbamate resins are synthesized by reacting an isocyanate- functional material with glycidol.
  • glycidol is very expensive and has various health hazards associated with it.
  • the present invention reduces or eliminates problems inherent in the art by providing a dual-cure epoxy and cyclic carbonate-containing urethane compound comprising an oxidized cyclic carbonate containing allyl-functional-carbamate which comprises a reaction product of a cyclic carbonate containing allyl-functional-carbamate, a ketone, water, and a base, optionally in the presence of a solvent, wherein, the cyclic carbonate containing allyl-functional-carbamate comprises a reaction product of an isocyanate-functional compound with (a) a cyclic carbonate compound having a hydroxyl group, and (b) one selected from the group consisting of, (bl) allyl alcohol, and (b2) a compound of the formula: HA-B-(X) n wherein, A is O, N, or S, n is an integer from 1 to 3, B is a linear or branched C1-C15 alkyl group, and X is
  • FIG. 1 provides the synthetic route for POLYISO A-glycidyl carbamate resin containing cyclic carbonate groups
  • FIG. 2 depicts the 13 C NMR spectra of POLYISO A-allyl GLC carbamate and POLYISO A-GLC-GC resins;
  • FIG. 3 shows ATR-FTIR spectra of POLYISO A-GLC-allyl carbamate and POLYISO A-GLC-GC resin.
  • any numerical range recited in this specification is intended to include all subranges of the same numerical precision subsumed within the recited range.
  • a range of “1.0 to 10.0” is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6.
  • Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein.
  • the present invention is directed to a dual-cure epoxy and cyclic carbonate-containing urethane compound comprising an oxidized cyclic carbonate containing allyl-functional-carbamate which comprises a reaction product of a cyclic carbonate containing allyl-functional-carbamate, a ketone, water, and a base, optionally a solvent, wherein, the cyclic carbonate containing allyl-functional-carbamate comprises a reaction product of an isocyanate-functional compound with (a) a cyclic carbonate compound having a hydroxyl group, and (b) one selected from the group consisting of (bl) allyl alcohol, and (b2) a compound of the formula HA-B-(X) n wherein, A is O, N, or S, n is an integer from 1 to
  • the present invention is directed to a thermoset polymer comprising a reaction product of the dual-cure epoxy and cyclic carbonate-containing urethane compound according to one of the first or second aspects and a curing agent.
  • the present invention is directed to one of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the dual-cure epoxy and cyclic carbonate-containing urethane compound according to one of the first or second aspects and a curing agent.
  • dual-cure epoxy and cyclic carbonate-containing urethane compounds can be synthesized by reacting an isocyanate with a compound containing one hydroxyl group and a cyclic carbonate group and another compound containing either one hydroxyl group and an epoxy group or one hydroxyl group and one or more allyl groups followed by epoxidizing the carbon-carbon double bond of the allyl group(s) using dioxirane epoxidation.
  • the resulting dual-cure epoxy and cyclic carbonate-containing urethane compounds can be cured into thermosetting coatings by reaction with curing agents reactive with both cyclic carbonate and epoxy groups.
  • These dual-cure epoxy and cyclic carbonate-containing urethane compounds may be prepared by several processes.
  • a glycidyl carbamate resin is a two-step process according to the reaction scheme below: first the isocyanate is reacted with allyl alcohol and then the product is oxidized to the epoxy group. Allyl alcohol is an inexpensive reagent that can be added to an isocyanate in a first step to form an allyl carbamate compound. In a second step, oxidation (epoxidation) of the double bond converts the allyl carbamate into a glycidyl carbamate.
  • an epoxy urethane can be made from a first reaction of an isocyanate-functional compound with a compound containing a hydroxyl group and one or more allyl groups.
  • the allyl groups are subsequently oxidized to covert the double bonds to epoxy groups as shown below.
  • a dual-cure polyurethane resin containing epoxy -functional groups and cyclic carbonate-functional groups may be made from the reaction of an isocyanate-functional compound with a compound containing a hydroxyl group and one or more cyclic carbonate groups as well as with a compound containing a hydroxyl group and one or more allyl groups.
  • the allyl groups are subsequently oxidized to covert the double bonds to epoxy groups as shown below.
  • An alternative method for epoxidizing olefins involves dioxirane, which can be generated in situ from the reaction of a ketone with potassium peroxymonosulfate, also known as potassium caroate (potassium monoperoxysulfate) or oxone (J. Org. Chem. 45, 4758-4760 (1980)).
  • potassium peroxymonosulfate also known as potassium caroate (potassium monoperoxysulfate) or oxone
  • polymer encompasses prepolymers, oligomers, and both homopolymers and copolymers; the prefix “poly” in this context refers to two or more.
  • molecular weight when used in reference to a polymer, refers to the number average molecular weight, unless otherwise specified.
  • polyol refers to compounds comprising at least two free hydroxyl groups. Polyols include polymers comprising pendant and terminal hydroxyl groups.
  • coating composition refers to a mixture of chemical components that will cure and form a coating when applied to a substrate.
  • adheresive or “adhesive composition” refer to any substance that can adhere or bond two items together. Implicit in the definition of an “adhesive composition” or “adhesive formulation” is the concept that the composition or formulation is a combination or mixture of more than one species, component or compound, which can include adhesive monomers, oligomers, and polymers along with other materials.
  • a “sealant” or “sealant composition” refers to a composition which may be applied to one or more surfaces to form a protective barrier, for example to prevent ingress or egress of solid, liquid or gaseous material or alternatively to allow selective permeability through the barrier to gas and liquid. In particular, it may provide a seal between surfaces.
  • a “casting” or “casting composition” refers to a mixture of liquid chemical components which is usually poured into a mold containing a hollow cavity of the desired shape, and then allowed to solidify.
  • a “composite” or “composite composition” refers to a material made from one or more polymers, containing at least one other type of material (e.g., a fiber) which retains its identity while contributing desirable properties to the composite.
  • a composite has different properties from those of the individual polymers/materials which make it up.
  • cured refers to components and mixtures obtained from reactive curable original compound(s) or mixture(s) thereof which have undergone chemical and/or physical changes such that the original compound(s) or mixture(s) is(are) transformed into a solid, substantially non-flowing material.
  • a typical curing process may involve crosslinking.
  • curable means that an original compound(s) or composition material(s) can be transformed into a solid, substantially non-flowing material by means of chemical reaction, crosslinking, radiation crosslinking, or the like.
  • compositions of the invention are curable, but unless otherwise specified, the original compound(s) or composition material(s) is(are) not cured.
  • the components useful in the present invention comprise a polyisocyanate.
  • polyisocyanate refers to compounds comprising at least two unreacted isocyanate groups, such as three or more unreacted isocyanate groups.
  • the polyisocyanate may comprise diisocyanates such as linear aliphatic polyisocyanates, aromatic polyisocyanates, cycloaliphatic polyisocyanates and aralkyl polyisocyanates.
  • isocyanate compounds that have two or more isocyanate groups, so that the final cyclic carbonate and epoxy -functional urethane compound can be cured into a thermoset material.
  • diisocyanate compounds include 1,6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, methylene diphenyl diisocyanate, isophorone diisocyanate, bis(4-isocyanatocyclohexyl) methane, tetramethylxylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2,2,4- and 2,4,4- trimethyl- 1,6- hexamethylene diisocyanate, and 4-isocyanatomethyl-l,8-octane diisocyanate.
  • Polyisocyanate compounds can also be used including the biuret and isocyanurate adducts of diisocyanates, polyisocyanates made by reacting a polyol with a diisocyanate, uretdione adducts, and allophanate polyisocyanates.
  • polyisocyanate that can be used is one prepared by the free radical copolymerization of a compound containing an isocyanate and a carbon-carbon double bond that can be polymerized using a free radical chain growth polymerization.
  • examples are m- TMI (a,a-dimethyl meta-isopropenyl benzyl isocyanate) and isocyanato ethyl methacrylate (IEM). These monomers can be combined with others in a copolymerization to yield a polymer having multiple isocyanate groups.
  • An isocyanate-functional compound having a uretdione may be used.
  • the uretdione from hexamethylene diisocyanate may be used:
  • Examples of compounds having the formula HA-B-(X) n are trimethylolpropane diallyl ether, ethylene glycol monoallyl ether, 3-butene-l-ol, 4-pentene-l-ol, 4-methyl-3- pentene-l-ol, 5-hexene-l-ol, 4-hexene-l-ol, 3 -hexene- l-ol, 4-methyl-3-hexene-l-ol, 2-ethyl- 4-pentene-l-ol, oleyl alcohol, and the like.
  • Examples of cyclic carbonate compounds containing a hydroxyl group include glycerin carbonate (4-(hydroxymethyl)-l,3-dioxolan-2-one), 5-hydroxy-l,3-dioxan-2-one, 5- ethyl-5-(hydroxymethyl)-l,3-dioxane-2-one, 5 methyl-5-(hydroxymethyl)-l,3-dioxane-2-one, and the like.
  • the first step may occur in the absence or presence of solvent and in the absence of presence of a catalyst.
  • Suitable solvents include toluene, xylenes, n-butyl acetate, t-butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl amyl ketone, dihydrolevoglucosenone (CYRENE), N-methyl 2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, diethyl ether, dimethylsulfoxide, dimethyl formamide, and dimethylacetamide. It is preferred to carry out the reaction in the absence of solvent, or, if solvent is needed due to viscosity, to use a solvent that can be readily removed after the reaction is complete.
  • Catalysts for the reaction include tin compounds such as dibutyl tin dilaurate, dibutyl tin diacetate, tertiary amines such as l,4-diazabicyclo[2.2.2]octane (DABCO) and other metal salts based on bismuth, iron, zirconium, or zinc. It is preferred to carry out the reaction without a catalyst or with a tin-based catalyst.
  • tin compounds such as dibutyl tin dilaurate, dibutyl tin diacetate, tertiary amines such as l,4-diazabicyclo[2.2.2]octane (DABCO) and other metal salts based on bismuth, iron, zirconium, or zinc. It is preferred to carry out the reaction without a catalyst or with a tin-based catalyst.
  • step two After reacting the isocyanate, step two, epoxidation of the double bond to an epoxide occurs in a two-phase (biphasic) system.
  • the allyl carbamate synthesized in step one is dissolved in a solvent.
  • the solvent is a ketone so that it can function as the source of ketone for the formation of the di oxirane.
  • Solvents such as acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone can be used, with acetone being the preferred solvent.
  • a mixture of a ketone and another solvent may also be used. Suitable solvents are those listed above for the isocyanate-allyl alcohol reaction.
  • a base is needed in the aqueous phase to maintain basic conditions to stabilize the dimethyldioxirane.
  • Inorganic bases such as sodium hydrogen carbonate (sodium bicarbonate), sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and the like may be used, with sodium bicarbonate being preferred.
  • the biphasic reaction mixture may be stirred vigorously to create interfacial surface area between the organic and aqueous phases.
  • An oxidant (oxone) is dissolved in water and added slowly to the reaction mixture.
  • a slow addition rate is preferred to yield the highest conversion of allyl groups to glycidyl groups.
  • the reaction can occur at temperatures ranging from 2 °C to 90 °C, with ambient temperature of 18-25 °C being preferred.
  • phase transfer catalyst can be used.
  • Suitable phase transfer catalysts include tetrabutyl ammonium hydrogen sulfate, quaternary ammonium compounds such as benzyl triethyl ammonium chloride, and the like.
  • Ionic liquids can also function as phase transfer compounds such as l-dodecyl-3-methylimidazolium tetrafluoroborate (DoDMIImBF4).
  • Crown ethers such as 18-crown-6 can also be used as a phase transfer catalyst.
  • an organic solvent is added to extract the product from the reaction mixture and the organic and aqueous layers are separated.
  • the organic layer is washed several times with aqueous sodium chloride and then the organic layer is separated from the aqueous layer, and the solvent removed by evaporation to yield the epoxy urethane resin.
  • Formulations may be prepared with the dual-cure epoxy and cyclic carbonate- containing urethane compounds and a multifunctional amine curing agent and, optionally, catalysts, solvents, additives, pigments.
  • Each of the epoxy and cyclic carbonate functional groups may react with the amine curing agents as shown below.
  • Suitable amine curing agents are those which are soluble or miscible in a coating composition of the invention.
  • Amine curing agents known in the art include, for example, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine, etc.
  • cycloaliphatic amine curing agents include, but are not limited to, 1,2- and 1,3-diaminocyclohexane, l,4-diamino-2,5- di ethylcyclohexane, l,4-diamino-3,6-di ethylcyclohexane, l,2-diamino-4-ethylcyclohexane,
  • araliphatic amines in particular those amines are employed in which the amino groups are present on the aliphatic radical for example m- and p-xylylenediamine, or their hydrogenation products as well as diamide diphenylmethane, diamide diphenylsulfonic acid (amine adduct), 4,4'-methylenedianiline, 2,4-bis(p- aminobenzyl)aniline, diethyltoluenediamine, and m-phenylene diamine.
  • the amine curing agents may be used alone or as mixtures.
  • Suitable amine-epoxide adducts are, for example, reaction products of diamines such as, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, m- xylylenediamine and/or bis(aminomethyl)cyclohexane with terminal epoxides such as, for example, polyglycidyl ethers of polyhydric phenols listed above.
  • diamines such as, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, m- xylylenediamine and/or bis(aminomethyl)cyclohexane
  • terminal epoxides such as, for example, polyglycidyl ethers of polyhydric phenols listed above.
  • amine curing agents used with the coating formulations of the invention are PACM (bis(para-aminocyclohexyl)methane), diethylene triamine (DETA), and 4,4'-methylene dianiline (MDA).
  • Stoichiometry ratios of amine to oxirane of the coating compositions may be based on amine hydrogen equivalent weight (AHEW) and on weight per epoxide (WPE).
  • a formulation of 1:1 was based on one epoxide reacted with one amine active hydrogen.
  • Solvents may be used in the formulation of the thermosets of the invention. Suitable solvents can include toluene, xylenes, n-butyl acetate, t-butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl amyl ketone, dihydrolevoglucosenone (CYRENE), N- methyl 2-pyrrolidone, N-ethyl-2-pyrrolidone, ethyl ethoxy propionate, tetrahydrofuran, diethyl ether, dimethylsulfoxide, dimethyl formamide, and dimethylacetamide. Curing can occur at ambient conditions or at elevated temperatures.
  • Curing may occur at ambient or low temperatures.
  • low temperatures the present inventors mean temperatures lower than room temperature, in some embodiments, between ambient temperature and 0 °C, in certain embodiments between 20 °C and 2 °C, in selected embodiments between 10 °C and 4 °C.
  • a coating composition of the invention may further contain at least one coating additive to, for example, enhance the composition's coating efficiency.
  • suitable coating additives include, but are not limited to, leveling and flow control agents such as silicones, fluorocarbons or cellulosics; extenders; plasticizers; flattening agents; pigment wetting and dispersing agents; ultraviolet (UV) absorbers; UV light stabilizers; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; antiflooding and anti-floating agents; and corrosion inhibitors.
  • leveling and flow control agents such as silicones, fluorocarbons or cellulosics; extenders; plasticizers; flattening agents; pigment wetting and dispersing agents; ultraviolet (UV) absorbers; UV light stabilizers; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; antiflooding and anti-
  • flattening agents include, but are not limited to, synthetic silica, available from the Davison Chemical Division ofW. R. Grace & Company as SYLOID, polypropylene, available from Hercules Inc., as HERCOFLAT, synthetic silicate, available from J. M. Huber Corporation, as ZEOLEX.
  • viscosity, suspension, and flow control agents include, but are not limited to, polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkylene amine salts of an unsaturated fatty acid, all available from BYK Chemie U.S.A, as ANTI TERRA.
  • Further examples include, but are not limited to, polysiloxane copolymers, polyacrylate solution, cellulose esters, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide wax, polyolefin wax, hydroxypropyl methyl cellulose, polyethylene oxide, and the like.
  • the inventive compositions may be applied to various substrates including, but not limited to, metals (e.g., aluminum, steel), plastics, ceramics, glass, natural materials, and concrete.
  • the substrates may optionally be cleaned prior to coating to remove processing oils or other contaminants.
  • the substrates may also be pretreated to improve adhesion and corrosion resistance.
  • a primer may be applied first to the substrate followed by application of the coating of the invention.
  • the coating of the invention can be applied to the substrate first, followed by a topcoat of another or similar material.
  • compositions of the invention may be contacted with a substrate by any methods known to those skilled in the art, including but not limited to, spraying, dipping, flow coating, rolling, brushing, pouring, squeegeeing, and the like.
  • inventive compositions may be applied in the form of paints or lacquers onto any compatible substrate.
  • the inventive composition is applied as a single layer.
  • the composition of the present invention may be applied as multiple layers as needed.
  • the coatings of the invention may be applied to various substrates including aluminum, steel, concrete, and plastic.
  • the substrates may be cleaned to remove processing oils or other contaminants prior to coating.
  • the substrates may also be pretreated to improve adhesion and corrosion resistance.
  • a primer may be applied first to the substrate followed by application of the coating of the invention.
  • the coating of the invention can be applied to the substrate first, followed by a topcoat of another or similar technology.
  • POLYISO A a polyfunctional aliphatic isocyanate resin based on hexamethylene diisocyanate (HDI) having an NCO content of 19.5 ⁇ 0.5% and a viscosity of 450 ⁇ 150 mPa s @ 25 °C; commercially available from Covestro LLC as DESMODUR N31100;
  • HDI hexamethylene diisocyanate
  • GLC glycerin carbonate commercially available from Huntsman as JEFFSOL GC;
  • DBTDL dibutyltin dilaurate 95%
  • OXIDANT A potassium peroxysulfate, commercially available from Sigma-Aldrich as OXONE;
  • CROSSLINKER A para-aminocyclohexyl methane (PACM), commercially available from Evonik;
  • SOLVENT B dichloromethane commercially available from Alfa Aesar
  • BRINE saturated aqueous solution of NaCl prepared by dissolving 500 g NaCl (certified ACS, Sigma-Aldrich) into 1 L of DI water at room temperature.
  • Epoxide equivalent weight (EEW, g/eq) of the epoxy products was determined by epoxy titration according to ASTM D1652-11 (2019). Impact tests were measured according to ASTM D2794 -93 (2019) with a BYK-GARDNER Heavy Duty Impact Tester Model IG- 1120, with a 1.8 kg (4 lb.) mass and 1.27 cm (0.5 in.) diameter round-nose punch. MEK double rubs of the cured film were determined according to ASTM D5402-19. Coatings that passed 400 double rubs without mar were considered fully cured. Film thickness was measured with a BYKO-TEST 8500. Konig pendulum hardness and pencil hardness were determined according to ASTM D4366-16 (2021) and ASTM D3363-20, respectively. The adhesion of coatings on steel substrate was evaluated using crosshatch adhesion ASTM D3359-17.
  • FIG. 2 is the 13 C NMR spectrum of POLYISO A-allyl GC (glycidyl carbamate) resin.
  • FIG. 3 is the ATR-FTIR spectrum of POLYISO A-allyl GC (glycidyl carbamate) resin.
  • FIG. 2 is the 13 C NMR spectrum of POLYISO A-GLC-GC resin.
  • ATR-FTIR 3338, 2934, 2860, 1796, 1708, 1683, 1527, 1463, 1403, 1372, 1239, 1175, 1089, 1047, 908, 859, 766, 714 cm .
  • FIG. 3 is the ATR-FTIR spectrum of POLYISO A-GLC-GC resin.
  • the POLYISO A-GLC-GC resin from Ex. 1 was mixed with CROSSLINKER A at different molar ratios (1 :2 and 1 :4).
  • the coating formulations were applied on to iron phosphate pretreated 22-gauge steel test panels purchased from Q-PANEL. Coating application was made using a drawdown bar for a final dry film thickness of approximately 80 pm. Coated panels were cured at room temperature for six days and placed in an oven at 80 °C for 45 minutes. The results of the coating evaluation are shown in Table I.
  • a dual-cure epoxy and cyclic carbonate-containing urethane compound comprising an oxidized cyclic carbonate containing allyl-functional-carbamate which comprises a reaction product of a cyclic carbonate containing allyl-functional-carbamate, a ketone, water, and a base, optionally a solvent, wherein, the cyclic carbonate containing allyl- functional-carbamate comprises a reaction product of an isocyanate-functional compound with (a) a cyclic carbonate compound having a hydroxyl group, and (b) one selected from the group consisting of (bl) allyl alcohol, and (b2) a compound of the formula HA-B-(X)n wherein, A is O, N, or S, n is an integer from 1 to 3, B is a linear or branched C1-C15 alkyl group, and X
  • Clause 3 The dual-cure epoxy and cyclic carbonate-containing urethane compound according to one of Clauses 1 and 2, wherein the compound having the formula HA-B-(X) n (I) is selected from the group consisting of trimethylolpropane diallyl ether, ethylene glycol monoallyl ether, 3 -butene- l-ol, 4-pentene-l-ol, 4-methyl-3 -pentene- l-ol, 5- hexene-l-ol, 4-hexene-l-ol, 3 -hexene- l-ol, 4-methyl-3-hexene-l-ol, 2-ethyl-4-pentene-l-ol, and oleyl alcohol.
  • the compound having the formula HA-B-(X) n (I) is selected from the group consisting of trimethylolpropane diallyl ether, ethylene glycol monoallyl ether, 3 -butene-
  • Clause 4 The dual-cure epoxy and cyclic carbonate-containing urethane compound according to any one of Clauses 1 to 3, wherein the base is selected from the group consisting of sodium hydrogen carbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and mixtures of any of these.
  • Clause 5 The dual-cure epoxy and cyclic carbonate-containing urethane compound according to any one of Clauses 1 to 4, wherein the reaction of the isocyanate- functional compound occurs in the presence of a catalyst selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, l,4-diazabicyclo[2.2.2]octane (DABCO), and metal salts based on bismuth, zirconium, or zinc.
  • a catalyst selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, l,4-diazabicyclo[2.2.2]octane (DABCO), and metal salts based on bismuth, zirconium, or zinc.
  • thermoset polymer comprising a reaction product of dual-cure epoxy and cyclic carbonate-containing urethane compound according to any one of Clauses 1 to 5 and a curing agent.
  • thermoset polymer according to Clause 6 wherein the curing agent comprises an amine curing agent selected from the group consisting of bis(para- aminocyclohexyl)methane, diethylene triamine, and 4,4'-methylene dianiline.
  • the curing agent comprises an amine curing agent selected from the group consisting of bis(para- aminocyclohexyl)methane, diethylene triamine, and 4,4'-methylene dianiline.
  • thermoset polymer according to Clause 6 wherein the dual-cure epoxy and cyclic carbonate-containing urethane compound is self-crosslinked.
  • thermoset polymer according to Clause 8 wherein selfcrosslinking comprises heating the dual-cure epoxy and cyclic carbonate-containing urethane compound to a temperature of from 20 °C to 100 °C.
  • Clause 10 One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the dual-cure epoxy and cyclic carbonate- containing urethane compound according to any one of Clauses 1 to 5.
  • Clause 13 The process according to one of Clauses 11 and 12, wherein the compound having the formula HA-B-(X) n is selected from the group consisting of trimethylolpropane diallyl ether, ethylene glycol monoallyl ether, 3-butene-l-ol, 4-pentene-l- ol, 4-methyl-3-pentene-l-ol, 5-hexene-l-ol, 4-hexene-l-ol, 3 -hexene- l-ol, 4-methyl-3- hexene-l-ol, 2-ethyl-4-pentene-l-ol, and oleyl alcohol.
  • the compound having the formula HA-B-(X) n is selected from the group consisting of trimethylolpropane diallyl ether, ethylene glycol monoallyl ether, 3-butene-l-ol, 4-pentene-l- ol, 4-methyl-3-pentene-l-ol, 5-
  • Clause 14 The process according to any one of Clause 11 tol3, wherein the base is selected from the group consisting of sodium hydrogen carbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and mixtures of any of these.
  • Clause 15 The process according to any one of Clauses 11 to 14, wherein reaction of the isocyanate-functional compound occurs in the presence of a catalyst selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, 1,4- diazabicyclo[2.2.2]octane (DABCO), and metal salts based on bismuth, zirconium, or zinc.
  • a catalyst selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, 1,4- diazabicyclo[2.2.2]octane (DABCO), and metal salts based on bismuth, zirconium, or zinc.
  • a thermoset polymer comprising a reaction product of the dual-cure epoxy and cyclic carbonate-containing urethane compound made according to the process of any one of Clauses 11 to 15 and a curing agent.
  • thermoset polymer according to Clause 16 wherein the curing agent comprises an amine curing agent selected from the group consisting of bis(para- aminocyclohexyl)methane, diethylene triamine, and 4,4'-methylene dianiline.
  • the curing agent comprises an amine curing agent selected from the group consisting of bis(para- aminocyclohexyl)methane, diethylene triamine, and 4,4'-methylene dianiline.
  • thermoset polymer according to Clause 16 wherein the dual-cure epoxy and cyclic carbonate-containing urethane compound is self-crosslinked.
  • thermoset polymer according to Clause 18, wherein selfcrosslinking comprises heating the dual-cure epoxy and cyclic carbonate-containing urethane compound to a temperature of from 20 °C to 100 °C.
  • Clause 20 One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the dual-cure epoxy and cyclic carbonate- containing urethane compound made according to the process of any one of Clauses 11 to 15.

Abstract

L'invention concerne un composé uréthane à double durcissement contenant de l'époxy et du carbonate cyclique comprenant un carbonate cyclique oxydé contenant un carbamate fonctionnel allyle qui comprend un produit de réaction d'un carbonate cyclique contenant du carbamate fonctionnel allyle, une cétone, de l'eau et une base, éventuellement un solvant, le carbonate cyclique contenant du carbamate fonctionnel allyle comprenant un produit de réaction d'un composé fonctionnel isocyanate avec (a) un composé carbonate cyclique ayant un groupe hydroxyle et (b) un élément choisi dans le groupe constitué par (b1) l'alcool allylique et (b2) un composé de formule HA-B-(X)n, et le composé uréthane à double durcissement contenant de l'époxy et du carbonate cyclique contenant des groupes fonctionnels époxy et carbonate cycliques. Le composé uréthane à double durcissement contenant de l'époxy et du carbonate cyclique de l'invention peut être utile dans la production de revêtements, d'adhésifs, de produits d'étanchéité, de films, d'élastomères, de pièces coulées et de mousses.
PCT/US2022/051904 2021-12-13 2022-12-06 Résines de polyuréthane à groupes fonctionnels époxy et carbonate cyclique et leurs polymères thermodurcissables WO2023114041A1 (fr)

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