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WO2023114015A1 - Nouveaux composés époxy-uréthane et leurs polymères thermodurcissables - Google Patents

Nouveaux composés époxy-uréthane et leurs polymères thermodurcissables Download PDF

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Publication number
WO2023114015A1
WO2023114015A1 PCT/US2022/051532 US2022051532W WO2023114015A1 WO 2023114015 A1 WO2023114015 A1 WO 2023114015A1 US 2022051532 W US2022051532 W US 2022051532W WO 2023114015 A1 WO2023114015 A1 WO 2023114015A1
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WO
WIPO (PCT)
Prior art keywords
diisocyanate
epoxy
isocyanato
methyl
cyclohexane
Prior art date
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PCT/US2022/051532
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English (en)
Inventor
Alan Ekin
Dean C. Webster
Jingbo Wu
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Covestro LLC
North Dakota State University NDSU
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Covestro LLC
North Dakota State University NDSU
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Priority claimed from EP22154900.9A external-priority patent/EP4223821A1/fr
Application filed by Covestro LLC, North Dakota State University NDSU filed Critical Covestro LLC
Publication of WO2023114015A1 publication Critical patent/WO2023114015A1/fr
Anticipated expiration legal-status Critical
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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/28—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
    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6407—Reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen
    • 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
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
    • 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
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/714—Monoisocyanates or monoisothiocyanates containing nitrogen in addition to isocyanate or isothiocyanate nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • 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
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates in general to polymers, and more specifically, to epoxy-urethane resins having a polyurethane backbone with epoxy-functional groups attached.
  • 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 (Hexion) or DER 331 (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.
  • pot life The time after mixing the components during which the coating can still be applied is known as the “pot life.”
  • 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. May, “Epoxy Resins: Chemistry and Technology”, 2 nd Edition, Routledge, 2018.
  • epoxy resins 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.
  • 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, although 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.
  • epoxy chemistry is well known and used extensively in the field of thermosetting materials for applications in coatings, composites, and adhesives. Having an epoxy-functional polyurethane can meet this need.
  • 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 discloses 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 (7. 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 (7. 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.
  • the present invention reduces or obviates problems inherent in the art by providing epoxy-urethane resins with epoxy-functional groups attached.
  • the resins of the invention may be cured with amines under ambient or elevated temperatures or undergo self-cure with heat.
  • the cured materials can be used for the production of coatings, adhesives, sealants, films, elastomers, castings, foams, and composites.
  • FIG. 1 is a diagram of the synthetic route to produce POLYISO A-EPOXY A RESIN;
  • FIG. 2 is the synthetic route to produce POLYISO B-EPOXY A RESIN;
  • FIG. 3 is the 13 C NMR spectra of POLYISO A- ALLYL ETHER A CARBAMATE and POLYISO A-EPOXY A RESIN;
  • FIG. 4 is the FTIR spectra of POLYISO A- ALLYL ETHER A CARBAMATE and POLYISO A-EPOXY A RESIN;
  • FIG. 5 is the 13 C NMR spectra of POLYISO B-ALLYL ETHER A CARBAMATE and POLYISO B-EPOXY A RESIN from EX. 2;
  • FIG. 6 is the ATR-FTIR spectra of POLYISO B-ALLYL ETHER A CARBAMATE and POLYISO B-EPOXY A RESIN;
  • FIG. 7 is a diagram of the synthetic route to produce POLYISO B-EPOXY B RESIN;
  • FIG. 8 is the 13 C NMR spectra of POLYISO B-ALLYL ETHER B CARBAMATE and POLYISO B-EPOXY B RESIN;
  • FIG. 9 is the ATR-FTIR spectra of POLYISO B-ALLYL ETHER B CARBAMATE and POLYISO B-EPOXY B 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 an entirely new approach to the synthesis of epoxy-functional polyurethanes that does not make use of glycidol, in which the epoxy group and the carbamate group are separated by more than one atom. This approach also results in epoxy-functional urethanes with novel compositions.
  • the synthesis method involves a first reaction of an isocyanate-functional compound with a compound containing a hydroxyl group and one or more vinyl groups. Next, the vinyl groups are oxidized to convert 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 or oxone (J. Org. Chem. 45, 4758-4760 (1980)). This method has been found to be useful in epoxidizing a number of different types of carbon-carbon double bonds (Org. Process Res. Dev., 6, 405-406 (2002); ACS Sustain. Chem. Eng., 6, 5115- 5121 (2016)).
  • 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 epoxyfunctional resin according to one of the previous two aspects.
  • 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.
  • Suitable polyisocyanates include aromatic, araliphatic, aliphatic or cycloaliphatic di- and/or polyisocyanates and mixtures thereof.
  • the polyisocyanate may comprise a diisocyanates of the formula R(NCO) 2 wherein R represents an aliphatic hydrocarbon residue having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon residue having 6 to 15 carbon atoms, an aromatic hydrocarbon residue having 6 to 15 carbon atoms or an araliphatic hydrocarbon residue having 7 to 15 carbon atoms.
  • an isocyanate-functional compound is reacted with a compound containing a hydroxyl, amine or thiol group and a vinyl group to form a vinyl-functional carbamate, urea or thiocarbamate.
  • a compound containing a hydroxyl, amine or thiol group and a vinyl group to form a vinyl-functional carbamate, urea or thiocarbamate.
  • isocyanate compounds that have two or more isocyanate groups, so that the final epoxy-functional carbamate composition can be cured into a thermoset material.
  • Example 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 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:
  • Suitable as compound B include, but are not limited to, the following, 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.
  • the first step can occur in the absence or presence of solvent and in the absence of presence of a catalyst.
  • Suitable solvents include, but are not limited to, 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 that the reaction occurs 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.
  • Optional 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.
  • DABCO l,4-diazabicyclo[2.2.2]octane
  • step two After reacting the isocyanate, step two, involving oxidation of the double bond to an epoxide occurs.
  • This reaction is a two-phase (biphasic) system.
  • the vinyl-functional 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 dioxirane.
  • 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, amine or thiol reaction.
  • a base in the aqueous phase serves to maintain basic conditions needed to stabilize the dioxirane.
  • Inorganic bases such as sodium hydrogen carbonate (sodium bicarbonate), sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and the like can be used.
  • Sodium bicarbonate is preferred.
  • the biphasic reaction mixture is stirred vigorously to create interfacial surface area between the organic and aqueous phases. Oxone is dissolved in water and added slowly to the reaction mixture. A slow addition rate is preferred to yield the highest conversion of vinyl groups to epoxy groups.
  • the reaction can occur at temperatures ranging from 2 °C to 90 °C. Ambient temperature of 18 °C to -25 °C is 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 allowed to separate.
  • the organic layer is washed several times with aqueous sodium chloride and separated from the aqueous layer and the solvent is removed by evaporation to yield the vinyl carbamate, urea or thiocarbamate resin.
  • compositions of the present invention may be used to provide coatings, adhesives, sealants, films, elastomers, castings, foams, and composites. Curing of the coatings, adhesives, sealants, films, elastomers, castings, foams, and composites of the invention may occur at ambient conditions or at elevated temperatures with a multifunctional amine curing agent or a curing agent reactive towards epoxy and, optionally, catalysts, solvents, additives, and pigments.
  • 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- diethylcyclohexane, l,4-diamino-3,6-diethylcyclohexane, 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 can be used in the formulation of the thermosets. 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.
  • CYRENE dihydrolevoglucosenone
  • 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.
  • Coatings, adhesives, sealants, films, elastomers, castings, foams, and composites compositions of the invention may further contain at least one additive to, for example, enhance the composition's 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, antisag and bodying agents; anti-skinning agents; anti-flooding 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,
  • flattening agents include, but are not limited to, synthetic silica, available from the Davison Chemical Division of W. 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.
  • POLYISO A an aliphatic isocyanate based on hexamethylene diisocyanate (HD I), commercially available from Covestro LLC (Pittsburgh, PA) as DESMODUR H (49.7% NCO);
  • POLYISO B an allophanate-modified polyisocyanate based on hexamethylene diisocyanate (HD I), commercially available from Covestro LLC (Pittsburgh, PA) as DESMODUR XP 2580 (19.3% NCO);
  • ALLYL ETHER A trimethylolpropane diallyl ether, commercially available from Perstorp Holding AB, Sweden as TMPDE 90;
  • DBTDL dibutyltin dilaurate 95%
  • OXIDANT A potassium peroxysulfate, commercially available from Alfa Aesar as OXONE;
  • CROSSLINKER A para-aminocyclohexyl methane (PACM) commercially available from Evonik;
  • SOLVENT B dichloromethane commercially available from Alfa Aesar
  • MEK methyl ethyl ketone commercially available from VWR International
  • BRINE saturated aqueous solution of NaCl prepared by dissolving
  • FIG. 4 is the 13 C NMR spectrum of the POLYISO A- ALLYL ETHER A CARBAMATE intermediate).
  • FIG. 4, lower panel, is the ATR-FTIR spectrum of the POLYISO A-ALLYL ETHER A CARBAMATE intermediate.
  • FIG. 3 upper panel is the 13 C NMR spectrum of the POLYISOCYANATE A-EPOXY A RESIN).
  • FIG. 4 upper panel is the FTIR spectrum of the POLYISO A-EPOXY A RESIN.
  • FIG. 5 shows the 13 C NMR spectrum of the POLYISO B-ALLYL ETHER A CARBAMATE intermediate.
  • the carbon-carbon double bond conversion was about 100% (analyzed by 13 C NMR spectroscopy, FIG. 5) and the yield was about 90%.
  • the viscosity of the resulting POLYISO B-EPOXY A RESIN was 31757 m Pa-s.
  • FIG. 5 lower panel is the 13 C NMR spectrum of the POLYISOCYANATE B-EPOXY A RESIN).
  • ATR-FTIR (neat) 3335, 2933, 2859, 1712, 1689, 1530, 1461, 1404, 1351, 1240, 1181, 1135, 1088, 991, 920, 752, 665cm 1 .
  • FIG. 6, lower panel, is the ATR-FTIR spectrum of the POLYISO B-ALLYL ETHER A CARBAMATE intermediate.
  • the carbon-carbon double bond conversion was about 100% (analyzed by 13 C NMR spectroscopy) and the yield was close to 100%.
  • the viscosity of the resulting POLYISO B-EPOXY A RESIN was 41826 mPa-s.
  • ATR-FTIR (neat) 3337, 2933, 2859, 1711, 1686, 1529, 1463, 1404, 1373, 1338, 1239, 1182, 1098, 1044, 908, 848, 778, 765.
  • FIG. 6, upper panel, is the ATR-FTIR spectrum of the POLYISO B-EPOXY A RESIN.
  • ATR-FTIR (cm 1 ) 3335, 2934, 2859, 1686, 1530, 1461, 1404, 1358, 1241, 1181, 1103, 1044, 994, 926, 749, 665.
  • FIG. 9, lower panel, is the ATR-FTIR spectrum of the POLYISO B -ALLYL ETHER B CARBAMATE.
  • FIG. 8 lower panel, is the 13 C NMR spectrum of the POLYISO B-EPOXY B RESIN).
  • ATR-FTIR (cm 1 ) 3335, 2933, 2860, 1684, 1528, 1462, 1404, 1360, 1240, 1181, 1105, 1046, 911, 855, 751, 665.
  • FIG. 9, upper panel is the ATR-FTIR spectrum of the POLYISO B-EPOXY B RESIN.
  • the POLYISO B-EPOXY A resin from Example 2 was mixed with CROSSLINKER A at three equivalent epoxy groups to NH groups ratios (1:1, 1:1.5, and 1:2, respectively) without using any solvent.
  • the coating formulations were applied onto 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 or placed in an oven at 80 °C as noted. The coatings were evaluated for physical properties and the results are provided in Table I.
  • RT cured at room temperature for 3 days; HT: cured at 80 °C for 45 minutes
  • Clause 3 The epoxy-functional resin according to one of Clauses 1 and 2, wherein (B) 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, oleyl alcohol, and mixtures of any of these.
  • B 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-
  • Clause 4 One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the epoxy-functional resin according to any one of Clauses 1 to 3.
  • Clause 5 A curable coating formulation comprising the epoxy-functional resin according to any one of Clauses 1 to 3 and a curing agent reactive with epoxy groups.
  • Clause 7 The curable coating formulation according to one of Clauses 5 and 6, wherein the curing agent is selected from the group consisting of PACM (bis(para- aminocyclohexyl)methane), diethylene triamine (DETA), 4,4'-methylene dianiline (MDA), and mixtures of any of these.
  • PACM bis(para- aminocyclohexyl)methane
  • DETA diethylene triamine
  • MDA 4,4'-methylene dianiline
  • Clause 10 The process according to one of Clauses 8 and 9, wherein (B) 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, oleyl alcohol, and mixtures of any of these.
  • B 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,
  • Clause 11 The process according to any one of Clauses 8 to 10, wherein the catalyst is selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, l,4-diazabicyclo[2.2.2]octane, and mixtures of any of these.
  • Clause 12 The process according to any one of Clauses 8 to 11, wherein the base is selected from the group consisting of sodium hydrogen carbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide, and mixtures of any of these.
  • Clause 13 The process according to any one of Clauses 8 to 12, wherein the ketone is selected from the group consisting of acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone, and mixtures of any of these.
  • Clause 14 One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the epoxy-functional resin made according to the process of any one of Clauses 8 to 13. [0125] Clause 15. A curable coating formulation comprising the epoxy-functional resin made according to the process of any one of Clauses 8 to 13 and a curing agent reactive with the epoxy groups.
  • Clause 16 The curable coating formulation according to Clause 15, wherein the curing agent is an amine-functional curing agent.
  • Clause 17 The curable coating formulation according to one of Clauses 15 and 16, wherein the curing agent is selected from the group consisting of PACM (bis(para- aminocyclohexyl)methane), diethylene triamine (DETA), 4,4'-methylene dianiline (MDA) and mixtures of any of these.
  • PACM bis(para- aminocyclohexyl)methane
  • DETA diethylene triamine
  • MDA 4,4'-methylene dianiline

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une résine à fonction époxy et son procédé de fabrication consistant à faire réagir un polyisocyanate ; et un composé : HX-Y-(Z)n dans lequel X représente O, N ou S, Y représente un groupe alkyle en C1-C15 linéaire ou ramifié, et Z représente -CH=CDE ou Z représente -F-O-G-CH=CDE, n représente un nombre entier de 1 à 3, dans laquelle D et E sont indépendamment choisis parmi H, un groupe alkyle en C1-C5 linéaire, et un groupe alkyle en C1-C5 ramifié, F et G sont indépendamment choisis parmi H, des groupes alkyle en C1-C15 linéaires ou ramifiés, pour former un carbamate, une urée ou un thiocarbamate à fonction vinyle ; à former un mélange contenant le carbamate, l'urée ou le thiocarbamate à fonction vinyle, une cétone, de l'eau et une base ; et à introduire une solution aqueuse d'oxone dans le mélange pour oxyder le carbamate, l'urée ou le thiocarbamate à fonction vinyle sur la résine à fonction époxy.
PCT/US2022/051532 2021-12-13 2022-12-01 Nouveaux composés époxy-uréthane et leurs polymères thermodurcissables Ceased WO2023114015A1 (fr)

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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830038A (en) 1957-05-07 1958-04-08 Du Pont Poly (polyalkylene ether urethane) polymers containing terminal epoxide groups
US3440230A (en) 1966-05-02 1969-04-22 Phillips Petroleum Co Self-contained,curable resins prepared by reacting organic isocyanates and epoxy alcohols
US3814578A (en) 1972-01-14 1974-06-04 Us Agriculture Treatment of textiles with glycidol-modified polyurethanes
DE2406996A1 (de) * 1974-02-14 1975-08-28 Basf Ag Hitzehaertbare ueberzugsmittel
US4699814A (en) 1986-10-06 1987-10-13 Ppg Industries, Inc. Color plus clear application of high solids thermosetting coating compositions containing epoxy-functional polyurethanes
US4749743A (en) 1986-10-06 1988-06-07 Ppg Industries, Inc. Epoxy-functional polyurethanes and high solids thermosetting coating compositions thereof
EP0553701A2 (fr) 1992-01-27 1993-08-04 BASF Corporation Polyuréthane à fonction époxy et composition de revêtement durcissable
US6849337B2 (en) * 2002-10-04 2005-02-01 Basf Corporation Powder coatings containing oxirane groups beta to urethane or urea groups
US7776956B2 (en) 2006-08-04 2010-08-17 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
US8097741B2 (en) 2007-03-30 2012-01-17 Ndsu Research Foundation Hybrid coatings prepared from glycidyl carbamate resins
US8852458B2 (en) 2007-12-12 2014-10-07 Ndsu Research Foundation Glycidyl carbamate coatings having improved corrosion resistance
US20150099128A1 (en) * 2012-04-18 2015-04-09 Ndsu Research Foundation Linear glycidyl carbamate (gc) resins for highly flexible coatings
US9051413B2 (en) 2007-09-28 2015-06-09 Ndsu Research Foundation Modified glycidyl carbamate resins
US9676895B2 (en) 2006-08-04 2017-06-13 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830038A (en) 1957-05-07 1958-04-08 Du Pont Poly (polyalkylene ether urethane) polymers containing terminal epoxide groups
US3440230A (en) 1966-05-02 1969-04-22 Phillips Petroleum Co Self-contained,curable resins prepared by reacting organic isocyanates and epoxy alcohols
US3814578A (en) 1972-01-14 1974-06-04 Us Agriculture Treatment of textiles with glycidol-modified polyurethanes
DE2406996A1 (de) * 1974-02-14 1975-08-28 Basf Ag Hitzehaertbare ueberzugsmittel
US4699814A (en) 1986-10-06 1987-10-13 Ppg Industries, Inc. Color plus clear application of high solids thermosetting coating compositions containing epoxy-functional polyurethanes
US4749743A (en) 1986-10-06 1988-06-07 Ppg Industries, Inc. Epoxy-functional polyurethanes and high solids thermosetting coating compositions thereof
EP0553701A2 (fr) 1992-01-27 1993-08-04 BASF Corporation Polyuréthane à fonction époxy et composition de revêtement durcissable
US6849337B2 (en) * 2002-10-04 2005-02-01 Basf Corporation Powder coatings containing oxirane groups beta to urethane or urea groups
US7776956B2 (en) 2006-08-04 2010-08-17 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
US9676895B2 (en) 2006-08-04 2017-06-13 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
US8097741B2 (en) 2007-03-30 2012-01-17 Ndsu Research Foundation Hybrid coatings prepared from glycidyl carbamate resins
US9051413B2 (en) 2007-09-28 2015-06-09 Ndsu Research Foundation Modified glycidyl carbamate resins
US9593258B2 (en) 2007-09-28 2017-03-14 Ndsu Research Foundation Modified glycidyl carbamate resins
US8852458B2 (en) 2007-12-12 2014-10-07 Ndsu Research Foundation Glycidyl carbamate coatings having improved corrosion resistance
US20150099128A1 (en) * 2012-04-18 2015-04-09 Ndsu Research Foundation Linear glycidyl carbamate (gc) resins for highly flexible coatings

Non-Patent Citations (27)

* Cited by examiner, † Cited by third party
Title
ACS SUSTAIN. CHEM. ENG., vol. 6, 2018, pages 5115 - 5121
CHEMSUSCHEM, vol. 12, no. 15, 2019, pages 3410 - 3430
EUR. POLYM. J., vol. 87, 2017, pages 535 - 552
J. AM. CHEM. SOC., vol. 120, 1998, pages 9513 - 9516
J. APPL. POLYM. SCI., vol. 52, 1994, pages 1137 - 1151
J. COAT. TECH. & RES., vol. 7, 2010, pages 531 - 546
J. COAT. TECH. RES., vol. 10, no. 2, 2012, pages 141 - 151
J. COAT. TECH. RES., vol. 6, 2011, pages 735 - 747
J. HETEROCYL. CHEM., vol. 7, 1970, pages 331 - 333
J. ORG. CHEM, vol. 24, 1992
J. ORG. CHEM., vol. 45, 1980, pages 4758 - 4760
J. POLYM. SCI. A POLYM. CHEM., vol. 43, 2005, pages 2985 - 2006
ORG. PROCESS RES. DEV., vol. 6, 2002, pages 405 - 406
POLYM. BULL., vol. 76, no. 6, 2019, pages 3233 - 3246
POLYMER. ADV. TECH., vol. 26, no. 7, 2015, pages 707 - 761
PROG. ORG. COAT, vol. 64, 2009, pages 128 - 137
PROG. ORG. COAT., vol. 57, 2006, pages 128 - 139
PROG. ORG. COAT., vol. 63, no. 4, 2008, pages 405 - 415
PROG. ORG. COAT., vol. 66, no. 1, 2009, pages 73 - 85
RSC ADV., vol. 3, no. 13, 2013, pages 4110 - 4129
SOLOUCK ET AL.: "synthesized isocyanate terminated prepolymers from difunctional polyols and diisocyanates that were then endcapped with glycidol. These were then cured with diamines to form crosslinked elastomers", IRAN. J. PHARMA. SCI., vol. 4, 2008, pages 281 - 288
SUN ET AL.: "studied the kinetics of the reaction of glycidol with isocyanate terminated prepolymers from aromatic and cycloaliphatic diisocyanates. The epoxy urethane terminated polymers were mixed with conventional BPA epoxy resins and cured and their underwater acoustic properties were studied", POLYM. BULL., vol. 69, 2012, pages 621 - 633
U. MEIER-WESTHUES: "Polyurethanes: Coatings, Adhesives and Sealants", VINCENTZ NETWORK, 2007
WEBSTER ET AL.: "studied the synthesis of glycidyl carbamate-functional resins made from the reaction of glycidol with multifunctional polyisocyanates derived from 1,6-hexamethylene diisocyanate (HDI). In one paper, the synthesis of multifunctional resins and their curing with amines to form coatings was studied", TCT RESEARCH, vol. 2, 2005, pages 517 - 528
YEGANEH ET AL.: "also studied polyurethane elastomers made from isocyanate terminated prepolymers capped with glycidol that were cured with a polyamic acid to form crosslinked elastomers", J. APPL. POLYM. SCI., vol. 103, 2007, pages 1776 - 1785
YEGANEH ET AL.: "also studied the curing of epoxy polyurethanes using a novel phenolic functionalized polyamide resin", HIGH PERF. POLYM., vol. 20, 2008, pages 126 - 145
YEGANEH ET AL.: "synthesized biodegradable epoxy terminated polyurethanes by end-capping of isocyanate terminated prepolymers with glycidol which were then cured with diamines to make thermosets", EUR. POLYM. J., vol. 41, 2005, pages 2370 - 2379

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