WO2023114645A1 - Nouveaux polyuréthanes ayant des groupes époxy latéraux et objets thermodurcis obtenus à partir d'eux - Google Patents

Nouveaux polyuréthanes ayant des groupes époxy latéraux et objets thermodurcis obtenus à partir d'eux Download PDF

Info

Publication number
WO2023114645A1
WO2023114645A1 PCT/US2022/080788 US2022080788W WO2023114645A1 WO 2023114645 A1 WO2023114645 A1 WO 2023114645A1 US 2022080788 W US2022080788 W US 2022080788W WO 2023114645 A1 WO2023114645 A1 WO 2023114645A1
Authority
WO
WIPO (PCT)
Prior art keywords
diisocyanate
bis
allyl
group
groups
Prior art date
Application number
PCT/US2022/080788
Other languages
English (en)
Inventor
Alan Ekin
Dean C. Webster
Jingbo Wu
Original Assignee
Covestro Llc
North Dakota State University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP22154902.5A external-priority patent/EP4223823A1/fr
Application filed by Covestro Llc, North Dakota State University filed Critical Covestro Llc
Publication of WO2023114645A1 publication Critical patent/WO2023114645A1/fr

Links

Classifications

    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/70—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
    • 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 polyurethanes having pendant epoxy groups and thermosets thereof.
  • 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 as 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.
  • 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. 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, 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. 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.
  • 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.
  • One approach to making epoxy-functional polyurethanes is that of glycidyl carbamate-functional resins. 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.
  • hydroxyl-functional polyepoxide is a diglycerol polyglycidyl ether having three epoxy groups per molecule.
  • the present invention provides polyurethanes with pendant epoxy groups of formula (I): wherein, R 1 is a linear or branched alkyl group, an allyl group, a glycidyl group, an aromatic group, a cycloaliphatic group, an alkyl-aromatic group, or mixtures thereof, R 2 is a linear aliphatic, a cycloaliphatic, an aromatic, or an alkyl aromatic group, R 3 is a hydrogen, a methyl, an ethyl, or other higher alkyl, an allyl oxy, a glycidyl oxy, an allyl oxy methyl, or a glycidyl oxy methyl group, and R 4 is an allyl oxy, a glycidyl oxy, an allyl oxy methyl, or a glycidyl oxy methyl group.
  • R 1 is a linear or branched alkyl group, an allyl group, a g
  • the invention further provides a process for producing the inventive polyurethanes with pendant epoxy groups, the process comprising (1) reacting a diisocyanate compound with a compound containing one or more allyl groups and two hydroxyl groups, to form a linear polyurethane having pendant allyl-functional groups; and (2) oxidizing the allyl groups to produce the polyurethane with pendant epoxy groups.
  • inventive polyurethanes may find use in coatings, adhesives, sealants, films, elastomers, castings, foams, and composites.
  • FIG. 1 illustrates the synthetic route to linear polyurethane epoxy resins
  • FIG. 2 is the 13 C NMR spectra of linear polymers Pl and P4;
  • FIG. 3 is the ATR-FTIR spectra of linear polymers P 1 and P4;
  • FIG. 4 is the 13 C NMR spectra of linear polymers P2 and P5;
  • FIG. 5 is the ATR-FTIR spectra of linear polymers P2 and P5;
  • FIG. 6 is the 13 C NMR spectra of linear polymers P3 and P6.
  • FIG. 7 is the ATR-FTIR spectra of linear polymers P3 and P6.
  • 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 polyurethane with pendant epoxy groups of formula (I): wherein, R 1 is a linear or branched alkyl group, an allyl group, a glycidyl group, an aromatic group, a cycloaliphatic group, an alkyl-aromatic group, or mixtures thereof, R 2 is a linear aliphatic, a cycloaliphatic, an aromatic, or an alkyl aromatic group, R 3 is a hydrogen, a methyl, an ethyl, or other higher alkyl, an allyl oxy, a glycidyl oxy, an allyl oxy methyl, or a glycidyl oxy methyl group, and R 4 is an allyl oxy, a glycidyl oxy, an allyl oxy methyl, or a glycidyl oxy methyl group.
  • R 1 is a linear or branched alkyl group, an allyl group,
  • the present invention is directed to a process for producing the polyurethane according to the previous paragraph, the process comprising (1) reacting a diisocyanate with a compound containing one or more allyl groups and two hydroxyl groups, to form a linear polyurethane having pendant allyl-functional groups; and (2) oxidizing the allyl groups to produce the polyurethane with pendant epoxy groups.
  • 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 polyurethane according to the previous two aspects.
  • the present inventors have unexpectedly discovered an entirely new approach to the synthesis of epoxy -functional polyurethanes that does not make use of glycidol, where an epoxy group is pendant to the polyurethane backbone and, optionally, at the end of the linear polyurethane chain.
  • the synthesis method involves a first reaction of a diisocyanate with a compound containing one or more allyl groups and two hydroxyl groups.
  • a monofunctional alcohol is also used to end cap the polyurethane.
  • the allyl groups are oxidized to covert the double bonds to epoxy groups.
  • An alternative method for epoxidizing olefins involves di oxirane, 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)).
  • polyurethanes having pendant epoxy groups can be synthesized by reacting a diisocyanate with a compound containing one or more allyl groups and two hydroxyl groups.
  • a monofunctional alcohol is also used to end cap the polyurethane.
  • the allyl groups are then oxidized to form epoxy groups.
  • the resulting epoxy -functional urethane compounds can be cured into thermosetting coatings by reaction.
  • 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.
  • organic diisocyanates which are particularly suitable for the present invention include 1 ,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-l,6-hexamethylene diisocyanate, 2, 4, 4-trimethyl- 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane- 1,3- and 1,4-diisocyanate, 1- isocyanato-2-isocyanato-methyl cyclopentane, l-isocyanato-3,3,5-trimethyl-5-isocyanato- methylcyclohexane (IPDI), bis-(4-isocyanatocyclohexyl)methane (HnMDI), 1,3- and 1,4- bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexxane, bis
  • diisocyanates may also be used.
  • Preferred diisocyanates include 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and bis(4-isocyanatocyclohexyl)- methane (HnMDI) because they are readily available and yield relatively low viscosity oligomers.
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • HnMDI bis(4-isocyanatocyclohexyl)- methane
  • Polyisocyanate adducts containing isocyanurate, iminooxadiazine dione, urethane, biuret, allophanate, uretdione and/or carbodiimide groups are also suitable for use in the present invention, and may be prepared from the same organic groups, R, described above.
  • Such polyisocyanates may have isocyanate functionalities of two to three or more and can be prepared, for example, by the trimerization or oligomerization of diisocyanates or by the reaction of diisocyanates with polyfunctional compounds containing hydroxyl or amine groups.
  • the polyisocyanate is the isocyanurate of hexamethylene diisocyanate, which may be prepared in accordance with U.S. Pat. No. 4,324,879, at col. 3, line 5 to col. 6, line 47.
  • An isocyanate-functional compound having a uretdione may be used.
  • the uretdione from hexamethylene diisocyanate may be used:
  • a diisocyanate compound is reacted with a compound containing one or more allyl groups and two hydroxyl groups along with a monofunctional alcohol to form a polyurethane having pendant allyl groups.
  • 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.
  • Examples of compounds having one or more allyl groups and two hydroxyl groups are trimethylolpropane monoallyl ether, trimethylolethane monoallyl ether, glycerol monoallyl ether, pentaerythritol diallyl ether and the like.
  • Examples of monofunctional alcohols include alkyl alcohols such as methanol, n- propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, t-butanol, n-pentanol, 2-ethyl hexanol, amyl alcohol, and the like; ether alcohols such as ethylene glycol methyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, and the like; cycloaliphatic alcohols such as cyclohexanol; aromatic alcohols such as phenol; aromatic aliphatic alcohols such as benzyl alcohol; allyl alcohol, trimethylolpropane diallyl ether, glycidol and the like.
  • alkyl alcohols such as methanol, n- propanol, iso-propanol, n-butanol, iso-butanol, sec-butano
  • the ratios of the diisocyanate, compound having one or more allyl groups and two hydroxyl groups and the monofunctional alcohol are adjusted such that the average value of n is 1 or greater.
  • the first step can be carried out in the absence or presence of solvent and in the absence of presence of a catalyst.
  • Possible solvents are 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 can 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 involving oxidation of the double bond to an epoxide is carried out.
  • the reaction is carried out in a two-phase (biphasic) system.
  • the polyurethane 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 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 allyl groups to glycidyl groups.
  • the reaction can be carried out 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 then 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 glycidyl carbamate resin.
  • Formulations are prepared with the polyurethanes having pendant epoxy groups and a multifunctional amine curing agent and, optionally, catalysts, solvents, additives, 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.
  • 2,2,4- and/or 2,4,4-trimethylhexamethylenediamine 1,2- and 1,3-diaminopropane; 2,2- dimethylpropylenediamine; 1,4-diaminobutane; 1,6-hexanediamine; 1,7-diaminoheptane; 1,8- diaminooctane; 1,9-diaminononae; 1,12-diaminododecane; 4-azaheptamethylenediamine; N,N'-bis(3-aminopropyl)butane-l,4-diamine; l-ethyl-l,3-propanediamine; 2,2(4),4-trimethyl- 1,6-hexanediamin; bis(3-aminopropyl)piperazine; N-aminoethylpiperazine; N,N-bis(3- aminopropyl)ethylenediamine; 2,4(6)-toluenediamine; dic
  • 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.
  • 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 be carried out 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.
  • 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.
  • 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, matting agents, pigment weting and dispersing agents, ultraviolet (UV) absorbers, UV light stabilizers, defoaming and antifoaming agents, anti-setling, 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, matting agents, pigment weting and dispersing agents, ultraviolet (UV) absorbers, UV light stabilizers, defoaming and antifoaming agents, anti-setling, anti-sag and bodying agents, anti-skinning agents, antiflooding and anti-
  • mating 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.
  • POLYISO A an aliphatic isocyanate based on hexamethylene diisocyanate (HDI), commercially available from Covestro LLC (Pittsburgh, PA) as DESMODUR H (49.7% 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 (OXONE), commercially available from Alfa Aesar;
  • SOLVENT B di chloromethane, commercially available from Alfa Aesar;
  • CROSSLINKER A para-aminocyclohexyl methane (PACM), commercially available from Evonik;
  • 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.
  • Step one synthesis of POLYISO A- ALLYL ETHER A linear polymer Pl
  • POLYISO A (33.8g 0.2 mol) and ALLYL ETHER A (26.3g, 0.15 mol) were added into a 500 mL three-neck round bottom flask equipped with a mechanical stirring apparatus, and CATALYST A (3 mg, 2 mmol) was added.
  • CATALYST A (3 mg, 2 mmol) was added.
  • the reaction mixture was stirred for about 2 hours and ALLYL ALCOHOL (5.8 g, 0.1 mol) was added into the reaction mixture.
  • SOLVENT B was added into reaction mixture to maintain stirring during polymerization.
  • Infrared spectroscopic analysis was performed to determine reaction completion by monitoring the disappearance of isocyanate peak at 2275 cm 4 .
  • the resulting POLYISO A- ALLYL ETHER A linear polymer Pl was directly and immediately used for the next step without purification.
  • ATR-FTIR (cm 4 ): 3326, 3063, 2932, 2859, 1691, 1521, 1462, 1238, 1135, 1094, 992, 925, 776,734, 702. (FIG. 3)
  • Step two synthesis of POLYISO A- ALLYL ETHER A linear polymer P4
  • the resulting POLYISO A- ALLYL ETHER A linear polymer Pl (containing about 0.217mol double bond), SOLVENT A (300mL), and BASE A (111 g, 6 equivalents, 1.32 mol) were added into a 2L three-neck, round bottom flask equipped with a mechanical stirring apparatus at once.
  • An aqueous solution (1.1 L) of OXIDANT A (267 g, 4 equivalents, 0.868 mol) was added dropwise at a flowrate of 1-2 mL min 1 using a pump at room temperature. After dropwise addition, the reaction solution was stirred at room temperature for another two hours.
  • the reaction mixture was liquid-liquid extracted with SOLVENT C (3 x 150 mL). The organic layer was separated and washed with saturated brine solution (3 x 100 mL), and the solvent removed by evaporation. The carbon-carbon double bond conversion was about 95% (analyzed by 13 C NMR spectroscopy, FIG. 2) and the yield was about 90%.
  • ATR-FTIR (cm’ 1 ): 3329, 2933, 2861, 1694, 1527, 1463, 1373, 1338, 1237, 1099, 1043, 907, 848, 776. (FIG. 3)
  • Step one Synthesis of POLYISO A- ALLYL ETHER A linear polymer P2
  • POLYISO A (30 g 0.178 mol) and ALLYL ETHER A (23.3 g, 0.134 mol) were added into a 500mL, three-neck, round bottom flask equipped with a mechanical stirring apparatus, CATALYST A (7.8 mg) was added. The reaction mixture was stirred for about two hours, dry SOLVENT E (2.8382 g, 0.0876 mol) was added into the reaction mixture. Dichloromethane was added into reaction mixture to maintain stirring during polymerization. Infrared spectroscopic analysis was performed to determine reaction completion by monitoring the disappearance of isocyanate peak at 2275 cm' 1 . The resulting POLYISO A- ALLYL ETHER A linear polymer P2 was directly and immediately used for next step without purification.
  • ATR-FTIR (cm' 1 ): 3334, 3011, 2934, 2859, 1694, 1519, 1463, 1237, 1136, 1095, 998, 926, 748, 665. (FIG. 5)
  • Step two Synthesis of POLYISO A- ALLYL ETHER A linear polymer P5
  • the resulting POLYISO A-ALLYL ETHER A linear polymer P2 (containing about 0.1338 mol double bond), SOLVENT A (300 mL), and BASE A (68 g 6 equiv, 0.803 mol) were added into a 2L three-neck, round bottom flask equipped with a mechanical stirring apparatus at once.
  • An aqueous solution (0.9 L) which contained OXIDANT A (165 g, 4 equiv, 0.535 mol) was added dropwise at a flowrate of 1-2 mL min 1 using a pump at room temperature. After dropwise addition, the reaction solution was stirred at room temperature for another two hours.
  • the reaction mixture was liquid-liquid extracted with SOLVENT C (3 x 150 mL). The organic layer was separated and washed with BRINE (3 X 100 mL), and evaporated. The carbon-carbon double bond conversion was about 95% (analyzed by 13 C NMR spectroscopy, FIG. 4) and the yield was about 90%.
  • ATR-FTIR (cm 4 ): 3327, 2932, 2861, 1692, 1527, 1462, 1411, 1338, 1239, 1099, 1040, 912, 850, 776, 729 (FIG. 5)
  • FIG. 6 [0103] ATR-FTIR (cm 4 ): 3334, 2933, 2861, 1696, 1519, 1462, 1412, 1237, 1096, 1047, 926, 749, 665. (FIG. 7)
  • Step two Synthesis of POLYISO A- ALLYL ETHER A linear polymer P6 [0104]
  • the resulting POLYISO A-ALLYL ETHER A linear polymer P3 (containing about 0.217 mol double bond), SOLVENT A (250 mL), and BASE A (111 g, 6 equiv, 1.32mol) were added into a 2L, three-neck, round bottom flask equipped with a mechanical stirring apparatus at once.
  • An aqueous solution (1.1 L) which contained OXIDANT A (267g, 4 equiv., 0.868 mol) was added dropwise at a flowrate of 1-2 mL min 1 using a pump at room temperature. After dropwise addition, the reaction solution was stirred at room temperature for another two hours.
  • the reaction mixture was liquid-liquid extracted with SOLVENT C (3 X 150 mL). The organic layer was separated and washed with BRINE (3 X 100 mL) and evaporated. The carbon-carbon double bond conversion was about 95% (analyzed by 13 C NMR spectroscopy, FIG. 6) and the yield was about 90%.
  • ATR-FTIR (cm 4 ): 3327, 2932, 2862, 1693, 1527, 1462, 1411, 1337, 1238, 1099, 1041, 910, 850, 753, 731. (FIG. 7
  • EPOXY RESIN P4 from Ex. 1 was mixed with CROSSLINKER A (the ratios of epoxy group and NH group are given in Table I) with SOLVENT D.
  • the resulting 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 80 °C for 45minutes.
  • Table I summarizes the coatings properties of EPOXY-FUNCTIONAL POLYURETHANE P4 cured with PACM.
  • EPOXY RESIN P5 from Ex. 2 was mixed with CROSSLINKER A (the ratios of epoxy group and NH group are as given in Table II) without 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 80 °C for 45minutes.
  • the coatings properties of EPOXY-FUNCTIONAL POLYURETHANE P5 cured with CROSSLINKER A are summarized in Table II.
  • EPOXY RESIN P6 from Example 3 was mixed with CROSSLINKER A (the ratios of epoxy group and NH group are as given in Table III) without 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 then cured at 80 °C for 45 min.
  • the coatings properties of EPOXY-FUNCTIONAL POLYURETHANE P6 cured with CROSSLINKER A are summarized in Table III.
  • a polyurethane with pendant epoxy groups according to formula (I): wherein, R 1 is a linear or branched alkyl group, an allyl group, a glycidyl group, an aromatic group, a cycloaliphatic group, an alkyl-aromatic group, or mixtures thereof, R 2 is a linear aliphatic, a cycloaliphatic, an aromatic, or an alkyl aromatic group, R 3 is a hydrogen, a methyl, an ethyl, or other higher alkyl, an allyl oxy, a glycidyl oxy, an allyl oxy methyl, or a glycidyl oxy methyl group, and R 4 is an allyl oxy, a glycidyl oxy, an allyl oxy methyl, or a glycidyl oxy methyl group.
  • Clause 2 One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the polyurethane according to Clause 1.
  • Clause 4 A process for producing the polyurethane according to Clause 1, the process comprising (1) reacting a diisocyanate with a compound containing one or more allyl groups and two hydroxyl groups, to form a linear polyurethane having pendant allyl- functional groups; and (2) oxidizing the allyl groups to produce the polyurethane with pendant epoxy groups.
  • Clause 6 The process according to one of Clauses 4 and 5, wherein the compound containing one or more allyl groups and two hydroxyl groups is selected from the group consisting of trimethylolpropane monoallyl ether, trimethylolethane monoallyl ether, glycerol monoallyl ether, pentaerythritol diallyl ether, or mixtures thereof.
  • Clause 7 The process according to one of Clauses 4 and 5, wherein step (1) occurs in the presence of a catalyst selected from the group consisting of dibutyl tin dilaurate and dibutyl tin diacetate.
  • Clause 8 A process for producing one of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite, the process comprising reacting the polyurethane according to Clause 1 with an amine curing agent.
  • Clause 9 The process according to Clause 8, wherein the amine curing agent is selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2,2,4- and/or 2,4,4-trimethylhexamethylenediamine, 1,2- and 1,3- diaminopropane, 2,2-dimethylpropylenediamine, 1 ,4-diaminobutane, 1 ,6-hexanediamine, 1,7- diaminoheptane, 1,8-diaminooctane, 1,9-diaminononae, 1,12-diaminododecane, 4- azaheptamethylenediamine, N,N'-bis(3-aminopropyl)butane-l,4-diamine, l-ethyl-1,3- propanediamine, 2,2(4),4-trimethyl-l,6-hexanediamin, bis(3-amin
  • 1,2- and 1,3- diaminocyclohexane 1,2- and 1,3- diaminocyclohexane, l,4-diamino-2,5-diethylcyclohexane, l,4-diamino-3,6- diethylcyclohexane, l,2-diamino-4-ethylcyclohexane, l,4-diamino-2,5-diethylcyclo-hexane, l,2-diamino-4-cyclohexylcyclohexane, isophorone-diamine, norboman ediamine, 4,4'- diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylethane, 4,4'- diaminodi cyclohexylpropane, 2,2-bis(4-aminocyclohexyl)propane, 3,3'
  • Clause 10 The process according to Clause 8, wherein the amine curing agent is selected from the group consisting of P ACM (bis(para-aminocyclohexyl)methane), diethylene triamine (DETA), and 4,4'-methylene dianiline (MDA).
  • P ACM bis(para-aminocyclohexyl)methane
  • DETA diethylene triamine
  • MDA 4,4'-methylene dianiline
  • Clause 11 A coating produced according the process of Clause 8.

Landscapes

  • 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 un polyuréthane comportant des groupes époxy latéraux. L'invention concerne également un procédé de production de ces polyuréthanes comportant des groupes époxy latéraux, le procédé comprenant (1) la réaction d'un diisocyanate avec un composé contenant un ou plusieurs groupes allyle et deux groupes hydroxyle, pour former un polyuréthane linéaire ayant des groupes latéraux à fonctionnalité allyle et (2) l'oxydation des groupes allyle pour produire le polyuréthane comportant des groupes époxy latéraux. Les polyuréthanes de la présente invention peuvent être incorporés dans des revêtements, des adhésifs, des agents d'étanchéité, des films, des élastomères, des pièces moulées, des mousses et des composites.
PCT/US2022/080788 2021-12-13 2022-12-02 Nouveaux polyuréthanes ayant des groupes époxy latéraux et objets thermodurcis obtenus à partir d'eux WO2023114645A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202163289040P 2021-12-13 2021-12-13
US63/289,040 2021-12-13
EP22154902.5 2022-02-03
EP22154902.5A EP4223823A1 (fr) 2022-02-03 2022-02-03 Nouveaux polyuréthanes comportant des groupes époxy pendants et leurs produits thermodurcis

Publications (1)

Publication Number Publication Date
WO2023114645A1 true WO2023114645A1 (fr) 2023-06-22

Family

ID=84887451

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2022/080788 WO2023114645A1 (fr) 2021-12-13 2022-12-02 Nouveaux polyuréthanes ayant des groupes époxy latéraux et objets thermodurcis obtenus à partir d'eux

Country Status (1)

Country Link
WO (1) WO2023114645A1 (fr)

Citations (16)

* 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
US4324879A (en) 1978-09-08 1982-04-13 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof
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
US5371148A (en) 1993-06-23 1994-12-06 Union Carbide Chemicals & Plastics Technology Corporation Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated carbodiimides
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 (17)

* 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
US4324879A (en) 1978-09-08 1982-04-13 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof
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
US5371148A (en) 1993-06-23 1994-12-06 Union Carbide Chemicals & Plastics Technology Corporation Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated carbodiimides
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
"Chemistry and Technology of Epoxy Resins", 1993, SPRINGER SCIENCE
"Raw Materials Index", NATIONAL PAINT & COATINGS ASSOCIATION
ACS SUSTAIN. CHEM. ENG., vol. 6, 2018, pages 5115 - 5121
CHEMSUSCHEM, vol. 12, no. 15, 2019, pages 3410 - 3430
EUR. POLYM. J., vol. 41, 2005, pages 2370 - 2379
EUROPEAN POLYMER JOURNAL, vol. 87, 2017, pages 535 - 552
HIGH PERF. POLYM., vol. 20, 2008, pages 126 - 145
IRAN. J. PHARMA. SCI., vol. 4, 2008, pages 281 - 288
J. AM. CHEM. SOC., vol. 120, 1998, pages 9513 - 9516
J. APPL. POLYM. SCI., vol. 103, 2007, pages 1776 - 1785
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, 1959, pages 1992
J. ORG. CHEM., vol. 45, 1980, pages 4758 - 4760
J. POLYM. SCI. A POLYM. CHEM., vol. 43, 2005, pages 2985 - 2006
JCT RESEARCH, vol. 2, 2005, pages 517 - 528
ORG. PROCESS RES. DEV, vol. 6, 2002, pages 405 - 406
POLYM. BULL., vol. 69, 2012, pages 621 - 633
POLYMER BULLETIN, vol. 76, no. 6, 2019, pages 3233 - 3246
POLYMERS FOR ADVANCED TECHNOLOGIES, vol. 26, no. 7, 2015, pages 707 - 761
PROG. ORG. COAT., vol. 57, 2006, pages 128 - 139
PROG. ORG. COAT., vol. 63, no. 4, 2008, pages 405 - 415
PROG. ORG. COAT., vol. 64, no. 2-3, 2009, pages 128 - 137
RSC ADVANCES, vol. 3, no. 13, 2013, pages 4110 - 4129

Similar Documents

Publication Publication Date Title
US9051413B2 (en) Modified glycidyl carbamate resins
US10899926B2 (en) Curable composition
US7776956B2 (en) Water dispersible epoxy urethane compounds and coating compositions
US20100285311A1 (en) Dual component (aqueous) hybrid reactive resin system, method for production and use thereof
US20150099128A1 (en) Linear glycidyl carbamate (gc) resins for highly flexible coatings
CA2505953C (fr) Composes acryliques et epoxydiques modifies par du silicone
KR102255314B1 (ko) 분무가능한 폴리우레탄 코팅
US20060047090A1 (en) Silicone modified polyurea
JP7440500B2 (ja) アスパラギン酸エステル官能性ポリシロキサン、それらの調製およびそれらの使用
JP5319454B2 (ja) 混合多脂環式アミン（ｍｐｃａ）及びｍｐｃａアルキレート
US8735526B2 (en) Polyenureas and method of making the same
EP4223823A1 (fr) Nouveaux polyuréthanes comportant des groupes époxy pendants et leurs produits thermodurcis
EP4223820A1 (fr) Composés d'urée glycidylique et leurs polymères thermodurcissables
EP4223825A1 (fr) Résines de polyuréthane à groupes fonctionnels époxy et carbonate cyclique et leurs polymères thermodurcissables
EP4223818A1 (fr) Composés époxy-uréthane et leur polymères thermodurcissables
EP4223819A1 (fr) Composés époxy-uréthane et leur polymères thermodurcissables
EP4223824A1 (fr) Nouveaux composés époxy-uréthane contenant de l'uretdione et leurs polymères thermodurcissables
WO2023114645A1 (fr) Nouveaux polyuréthanes ayant des groupes époxy latéraux et objets thermodurcis obtenus à partir d'eux
EP4223821A1 (fr) Nouveaux composés époxy-uréthane et leurs polymères thermodurcissables
EP4223822A1 (fr) Résines de carbamate de glycidyle et leurs polymères thermodurcissables
WO2023114041A1 (fr) Résines de polyuréthane à groupes fonctionnels époxy et carbonate cyclique et leurs polymères thermodurcissables
WO2023114013A1 (fr) Composés époxy-uréthane et leurs polymères thermodurcissables
WO2023114644A1 (fr) Résines de carbamate de glycidyle et leurs polymères thermodurcissables
EP4223817A1 (fr) Compositions d'époxy-uréthane durcissant à basse température
WO2023114015A1 (fr) Nouveaux composés époxy-uréthane et leurs polymères thermodurcissables

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22839603

Country of ref document: EP

Kind code of ref document: A1