FIELD OF THE INVENTION

[0001] The present invention relates in general to polymers, and more specifically, to thermosetting compositions made from glycidyl carbamate resins.

BACKGROUND OF THE INVENTION

[0002] High performance paint and coating systems are needed for many applications ranging from aircrafts, ships, chemical plants, flooring, bridges, and many others. Although there are many coatings binder systems available, the two most prominent are epoxy coating systems and polyurethane coating systems.

[0003] 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. Typically, 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. Because the reactions between the amine curing agent and the epoxy resin start as soon as the two ingredients are mixed, these materials are provided separately as two-component systems (2K) and are mixed just prior to application. The time after mixing the components during which the coating can still be applied is known as the “pot life.” Sometimes the pot life is defined as the time for the viscosity to double; however, the pot life for any given coating system is that time where the viscosity is suitable for application. More information about epoxy resin technology can be found in various reference materials including B. Ellis, ed., “Chemistry and Technology of Epoxy Resins”, Springer Science, 1993; H. Panda, “Epoxy Resins Technology Handbook”, 2 ^nd Revised Edition, Asia Pacific Business Press, 2019; C. May, “Epoxy Resins: Chemistry and Technology”, 2 ^nd Edition, Routledge, 2018.

[0004] In addition to amines, epoxy resins also react with themselves (homopolymerization), anhydrides, phenols, and/or thiols. An epoxy formulation may contain multiple different kinds of curing agents as well as the right conditions for homopolymerization.

[0005] Polyurethane coatings represent a class of high-performance systems that can be used for a number of different applications. Polyurethanes are highly desired for their durability, toughness, and abrasion resistance, which is believed to be a result of extensive hydrogen bonding. Two component (2K) polyurethane coatings involve the reaction of a polyol with a polyisocyanate. As with epoxy resins, the curing reactions start as soon as the components are mixed; therefore, the coating system is supplied in two packages that are mixed just prior to application. The polyol can be an acrylic polyol, a polyester polyol, a polyether polyol, a polyurethane polyol, or a polycarbonate polyol. The polyisocyanate component can be based on aromatic or aliphatic building blocks. Aromatic polyisocyanates react very rapidly, while aliphatic polyisocyanates react slower; however, it is possible to accelerate the curing with the use of catalysts. Aliphatic polyisocyanates are preferred for use where the coating requires weathering performance. More information about polyurethanes and their use in coatings can be found in various reference materials including “Szy cher’s Handbook of Polyurethanes”, 2 ^nd edition, CRC Press, 2012; U. Meier-Westhues, “Polyurethanes: Coatings, Adhesives and Sealants”, Vincentz Network, 2007.

[0006] However, due to concerns about exposure to isocyanates, there is a desire to be able to make polyurethanes without using isocyanates at the point of application. A number of approaches have been explored including cyclic carbonate-amine chemistry and carbamate-aldehyde chemistry, among others (Polym. Bull. 2019, 76 (6), 3233-3246; ChemSusChem 2019, 12 (15), 3410-3430; Eur. Polym. J. 2017, 87, 535-552; RSCAdv. 2013, 3 (13), 4110-4129; Polymer. Adv. Tech. 2015, 26 (7), 707-761).

[0007] In making new coatings systems, it is desirable to maintain the polyurethane character as the hydrogen bonding it affords imparts significant toughness, durability, and abrasion resistance. Therefore, a system that results in crosslinked polyurethane materials, but uses a different crosslinking chemistry is desirable.

[0008] As described previously, 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. [0009] One potential approach is the use of glycidyl carbamate chemistry. The glycidyl carbamate group is an epoxy group (glycidyl) attached to a carbamate (urethane) group. Resins containing multiple glycidyl carbamate groups can be cured into crosslinked coatings by reaction with multifunctional amine curatives. An advantage of this system is that urethane groups are present to take advantage of the abrasion resistance, toughness, and durability expected of polyurethane systems. Further, while polyisocyanates may be used in the synthesis of glycidyl carbamate-functional resins, the end user is not exposed to isocyanates.

[0010] Glycidyl carbamates are typically synthesized by the reaction of a polyisocyanate with glycidol. In U.S. Pat. No. 2,830,038, 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 produce an elastomer.

[0011] Doss, in U.S. Pat. No. 3,440,230, teaches the synthesis of a glycidyl carbamate resin by the reaction of a mixture of 2,4- and 2,6-toluene diisocyanate (TDI) with glycidol. The product can be cured at elevated temperature (180 °C for 30 minutes) between aluminum strips and produces an adhesive. Pittman et al. disclose glycidol-modified polyurethanes as treatments for textiles in U.S. Pat. No. 3,814,578. To prepare the glycidol-modified polyurethane, an isocyanate-terminated prepolymer was reacted with glycidol. The product is applied to a fabric either from solvent or as an aqueous emulsion and cured.

[0012] Several researchers have studied the rearrangement reactions of glycidyl carbamates. In an early report, Iwakura and Taneda indicate that N-substituted phenyl glycidyl carbamate would rearrange at elevated temperatures to 3-phenyl-5- hydroxytetrahydro-l,3-oxazin-2-one (J. Org. Chem, 24, 1992 (1959)). However, Farrisey and Nashu show that, when catalyzed by a tertiary amine, phenyl glycidyl carbamate rearranges at elevated temperatures to 3-phenyl-4-hydroxymethyl-2-oxazolidones (J. Heterocyl. Chem., 7, 331-333 (1970)). [0013] The group of Chen et al. report the synthesis of glycidol-terminated polyurethanes (glycidyl carbamates) and find that they had good adhesion at low temperatures as well as good storage stability and room temperature curing (J. Appl. Polym. Sci., 51, 1199-1206 (1994)). A subsequent study shows that the glycidol-terminated polyurethanes have better impact strength, fracture energy, and adhesion than a conventional epoxy resin (J. Appl. Polym. Sci., 52, 1137-1151 (1994)). In EP 0553701 A2, Rehfuss, et al. report a coating system made from reacting a polyisocyanate with glycidol to produce the glycidyl carbamate resin and then curing it with a polyfunctional acid compound. Yeganeh et al. synthesized biodegradable epoxy terminated polyurethanes by end-capping of isocyanate terminated prepolymers with glycidol which are cured with diamines to make thermosets (Eur. Polym. J. 41, 2370-2379 (2005); J. Polym. Sci. A Polym. Chem. 43, 2985-2006 (2005)). Yeganeh et al. also report polyurethane elastomers made from isocyanate terminated prepolymers capped with glycidol were cured with a polyamic acid to provide crosslinked elastomers (J. Appl. Polym. Sci. 103, 1776-1785 (2007)). Yeganeh et al. also studied the curing of epoxy polyurethanes using a novel phenolic functionalized polyamide resin (High Perf. Polym. 20, 126-145 (2008)). Solouck et al. synthesized isocyanate terminated prepolymers from difunctional polyols and diisocyanates that were then end-capped with glycidol. These were cured with diamines to produce crosslinked elastomers (Iran. J. Pharma. Sci., 4, 281-288 (2008)). 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. 69, 621-633 (2012)).

[0014] In a series of investigations, 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 (HD I). In one paper, the synthesis of multifunctional resins and their curing with amines to produce coatings was studied (JCT Research, 2, 517-528 (2005)). In another paper, the self-crosslinking reaction at elevated temperature was studied as were the properties of coatings cured with the selfcrosslinking reaction (Prog. Org. Coat., 57, 128-139(2006)). It was also shown that modification of the polyisocyanates with monofunctional alcohols, followed by reaction with glycidol could be used to moderate the viscosity of the resins. The resulting products could be cured with amines or through self-crosslinking to produce coatings (J. Coat. Tech. & Res., 7, 531-546 (2010); U.S. Pat. Nos. 9,051,413; and 9,593,258). Webster et al., also demonstrate in U.S. Pat. No. 8,852,458 that polyfunctional glycidyl-carbamate resins could be blended with conventional BPA epoxy resins to provide corrosion resistant coatings. 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). To make highly flexible coatings 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).

[0015] All these glycidyl carbamate resins are synthesized by reacting an isocyanate- functional material with glycidol. However, as those skilled in the art are aware, glycidol is very expensive and there are various health hazards associated with it. Because thermosets made from glycidyl carbamate-functional resins have the potential to possess very useful properties as coatings, adhesives and other materials, a method of making glycidyl carbamate-functional resins is needed that does not involve the use of glycidol.

[0016] To reduce or eliminate problems; therefore, a need exists in the art for a safe and effective method to synthesize glycidyl carbamate-functional resins. The method should be convenient and capable of being carried out at room temperature. It should utilize relatively safe compounds. The resultant synthesized glycidyl carbamate compounds should be curable into thermosetting coatings by reaction with curing agents which are reactive with epoxyfunctional groups.

SUMMARY OF THE INVENTION

[0017] Accordingly, the present invention obviates problems inherent in the art by providing a method to epoxidize allyl carbamates to glycidyl carbamates. This very convenient method may occur at room temperature, acetone can be used as both a solvent for the resin and the source of dimethyldioxirane, oxone (potassium peroxysulfate) is a relatively safe compound used for example in the disinfection of swimming pools, and sodium bicarbonate is a common and safe chemical. Conversion of allyl groups to epoxide groups is quantitative. Thus, a safe and effective method to synthesize glycidyl carbamate-functional resins has been found. The synthesized glycidyl carbamate compounds can be cured into thermosetting coatings by reaction with curing agents which are reactive with epoxyfunctional groups.

[0018] These and other advantages and benefits of the present invention will be apparent from the Detailed Description of the Invention herein below.

BRIEF DESCRIPTION OF THE FIGURES

[0019] The present invention will now be described for purposes of illustration and not limitation in conjunction with the figures, wherein:

[0020] FIG. 1 shows the synthetic route for POLYISOCYANATE A-GLYCIDYL CARBAMATE;

[0021] FIG. 2 illustrates the ¹³ C NMR spectrum of the epoxidation product of POLYISOCYANATE A-GLYCIDYL CARBAMATE using a m-CPBA system;

[0022] FIG. 3 shows the ¹³ C NMR spectrum of the epoxidation product of POLYISOCYANATE A-GLYCIDYL CARBAMATE using a H2O2 system;

[0023] FIG. 4 is the ¹³ C NMR spectrum of the epoxidation product of POLYISOCYANATE A-GLYCIDYL CARBAMATE using the inventive system;

[0024] FIG. 5 provides the synthetic route for a POLYISOCYANATE B-GLYCIDYL CARBAMATE;

[0025] FIG. 6A illustrates the ¹³ C NMR spectra of a POLYISOCYANATE B- GLYCIDYL CARBAMATE for large batch;

[0026] FIG. 6B illustrates the ¹³ C NMR spectra of a POLYISOCYANATE B- GLYCIDYL CARBAMATE for large batch; and

[0027] FIG. 7 shows the ATR-FTIR spectrum of a POLYISOCYANATE B-GLYCIDYL CARBAMATE.

DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will now be described for purposes of illustration and not limitation. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, and so forth in the specification are to be understood as being modified in all instances by the term “about.” [0029] Any numerical range recited in this specification is intended to include all subranges of the same numerical precision subsumed within the recited range. For example, 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. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification such that amending to expressly recite any such sub-ranges would comply with the requirements of 35 U.S.C. §112(a), and 35 U.S.C. §132(a). The various embodiments disclosed and described in this specification can comprise, consist of, or consist essentially of the features and characteristics as variously described herein.

[0030] Any patent, publication, or other disclosure material identified herein is incorporated by reference into this specification in its entirety unless otherwise indicated, but only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material expressly set forth in this specification. As such, and to the extent necessary, the express disclosure as set forth in this specification supersedes any conflicting material incorporated by reference herein. Any material, or portion thereof, that is said to be incorporated by reference into this specification, but which conflicts with existing definitions, statements, or other disclosure material set forth herein, is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material. Applicant reserves the right to amend this specification to expressly recite any subject matter, or portion thereof, incorporated by reference herein.

[0031] Reference throughout this specification to “various non-limiting embodiments,” “certain embodiments,” or the like, means that a particular feature or characteristic may be included in an embodiment. Thus, use of the phrase “in various non-limiting embodiments,” “in certain embodiments,” or the like, in this specification does not necessarily refer to a common embodiment, and may refer to different embodiments. Further, the particular features or characteristics may be combined in any suitable manner in one or more embodiments. Thus, the particular features or characteristics illustrated or described in connection with various or certain embodiments may be combined, in whole or in part, with the features or characteristics of one or more other embodiments without limitation. Such modifications and variations are intended to be included within the scope of the present specification.

[0032] The grammatical articles “a”, “an”, and “the”, as used herein, are intended to include “at least one” or “one or more”, unless otherwise indicated, even if “at least one” or “one or more” is expressly used in certain instances. Thus, these articles are used in this specification to refer to one or more than one (i. e. , to “at least one”) of the grammatical objects of the article. By way of example, and without limitation, “a component” means one or more components, and thus, possibly, more than one component is contemplated and may be employed or used in an implementation of the described embodiments. Further, the use of a singular noun includes the plural, and the use of a plural noun includes the singular, unless the context of the usage requires otherwise.

[0033] The present inventors have surprisingly discovered that an alternative to using glycidol in the synthesis of glycidyl carbamates is a two-step process of first reacting the isocyanate with allyl alcohol and then oxidizing it to the epoxy group as shown below. Allyl alcohol is an inexpensive reagent that can be added to an isocyanate in a first step to produce an allyl carbamate compound. In the second step, oxidation (epoxidation) of the double bond can convert the allyl carbamate into a glycidyl carbamate as shown in the reaction scheme below:

[0034] There are a number of approaches for converting terminal double bonds into epoxy groups. One of the more common approaches is to use m-chloroperbenzoic acid which reacts directly with a carbon-carbon double bond to convert it to the corresponding epoxide (J. Am. Chem. Soc., 120, 9513-9516 (1998)). However, the by-product of the reaction is m- chlorobenzoic acid in stoichiometric amounts, which creates significant waste. [0035] 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 (2018)).

[0036] Thus, in a first aspect, the present invention is directed to a glycidyl carbamate- functional composition comprising a reaction product of an allyl carbamate composition with a ketone, water, a base, and an aqueous solution of an oxidant, wherein the allyl carbamate composition comprises a reaction product of a polyisocyanate, allyl alcohol, and optionally a catalyst.

[0037] In a second aspect, the present invention is directed to a process for producing a glycidyl carbamate-functional composition, the process comprising reacting a polyisocyanate with allyl alcohol, optionally in the presence of a catalyst, to produce an allyl carbamate composition and combining the allyl carbamate composition with a ketone, water, a base, and an aqueous solution of an oxidant to produce the glycidyl carbamate-functional composition.

[0038] In a third aspect, the present invention is directed to a process of self-crosslinking the glycidyl carbamate-functional composition according to either of the previous two aspects at elevated temperatures.

[0039] In a fourth aspect, the present invention is directed to a process for producing a crosslinked thermoset polymer, the process comprising curing the glycidyl carbamate- functional composition according to one of the preceding three aspects with a curing agent reactive towards epoxy-functional groups.

[0040] In a fifth aspect, 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 glycidyl carbamate-functional composition according to one of the previous four aspects.

[0041] As used herein, the term “polymer” encompasses prepolymers, oligomers, and both homopolymers and copolymers; the prefix “poly” in this context refers to two or more. As used herein, the term “molecular weight”, when used in reference to a polymer, refers to the number average molecular weight, unless otherwise specified. [0042] As used herein, the term “polyol” refers to compounds comprising at least two free hydroxyl groups. Polyols include polymers comprising pendant and terminal hydroxyl groups.

[0043] As used herein, the term “coating composition” refers to a mixture of chemical components that will cure and produce a coating when applied to a substrate.

[0044] The terms “adhesive” 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.

[0045] A “sealant” or “sealant composition” refers to a composition which may be applied to one or more surfaces to produce 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.

[0046] 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.

[0047] 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.

[0048] The terms “cured,” “cured composition” or “cured compound” refer 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.

[0049] The term “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. Thus, compositions of the invention are curable, but unless otherwise specified, the original compound(s) or composition material(s) is(are) not cured. [0050] The components useful in the present invention comprise a polyisocyanate. As used herein, the term “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.

[0051] Suitable polyisocyanates include aromatic, araliphatic, aliphatic or cycloaliphatic di- and/or polyisocyanates and mixtures thereof. In certain embodiments, the poly isocyanate may comprise a diisocyanate 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.

[0052] Examples of the 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-l,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-cyclohexyl)-methane, a, a, a', a' -tetramethyl- 1,3- and 1,4-xylene diisocyanate, 1-isocyanato-l-methy 1-4(3)- isocyanato-methyl cyclohexane, and 2,4- and 2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentane diisocyanate (PDI) - biobased), and, isomers of any of these; or combinations of any of these. Mixtures of 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.

[0053] 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. In certain embodiments, 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.

[0054] An isocyanate-functional compound having a uretdione may be used. For example, the uretdione from hexamethylene diisocyanate may be used:

[0055] In various embodiments, the present invention relates to a process for synthesizing glycidyl carbamate-functional compositions.

[0056] In a first step, a polyisocyanate is reacted with allyl alcohol to produce allyl carbamate. Although in principle any polyisocyanate can be used, it is preferred to use polyisocyanates that have two or more isocyanate groups, so that the final glycidyl carbamate-functional composition can be cured into a thermoset material. The first step of the process of the invention may optionally occur in the presence of solvent and optionally in the 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 to conduct 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.

[0057] Suitable catalysts include, but are not limited to, 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.

[0058] After reacting the polyisocyanate, the second step of the inventive process is oxidation of the double bond to an epoxide. This occurs in a two phase (biphasic) system. The allyl carbamate synthesized in the first step is dissolved in a solvent. Preferably, 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 preferred. Mixtures of a ketone and another solvent may also be used. Suitable solvents include those listed herein for the polyisocyanateallyl alcohol reaction.

[0059] A base in the aqueous phase serves to maintain basic conditions needed to stabilize the dioxirane. Suitable inorganic bases include, but are not limited to, sodium hydrogen carbonate (sodium bicarbonate), sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and the like. Sodium bicarbonate is preferred. The biphasic reaction mixture is stirred vigorously to create an interfacial surface area between the organic phase and the aqueous phase. An oxidant, such as potassium peroxy sulfate, is dissolved in water and added slowly to the reaction mixture. The slow addition rate is preferred to yield the highest conversion of allyl groups to glycidyl groups. The reaction may occur at temperatures ranging from 2 °C to 90 °C with an ambient temperature of 18 °C to 25 °C being preferred.

[0060] Optionally, a phase transfer catalyst may be used. Suitable phase transfer catalysts include, but are not limited to, tetrabutyl ammonium hydrogen sulfate, quaternary ammonium compounds such as benzyl triethyl ammonium chloride, and the like. Ionic liquids may also function as phase transfer compounds such as l-dodecyl-3-methylimidazolium tetrafluoroborate (DoDMIImBF4). Crown ethers such as 18-crown-6 may also be used as a phase transfer catalyst in the present invention.

[0061] After completion of the reaction, 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 removed by evaporation to yield the glycidyl carbamate resin.

[0062] In various embodiments, the 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 -functional groups and, optionally, catalysts, solvents, additives, and pigments.

[0063] Suitable amine curing agents are those which are soluble or miscible in a coating composition of the invention. Amine curing agents known to those skilled in the art include, for example, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine, etc. as well as

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-l,6-hexanediamin, bis(3-aminopropyl)piperazine, N-aminoethylpiperazine, N,N- bis(3-aminopropyl)ethylenediamine, 2,4(6)-toluenediamine, dicyandiamine, melamine formaldehyde, tetraethylenepentamine;, 3-diethylaminopropylamine, 3,3"- iminobispropylamine, tetraethylenepentamine, 3-diethylaminopropylamine, and 2,2,4- and

2.4.4-trimethylhexamethylenediamine. Exemplary cycloaliphatic amine-curing agents include, but are not limited to, 1,2- and 1,3-diaminocyclohexane, l,4-diamino-2,5- di ethylcyclohexane, l,4-diamino-3,6-di ethylcyclohexane, l,2-diamino-4-ethylcyclohexane,

1.4-diamino-2,5-di ethylcyclo-hexane, l,2-diamino-4-cyclohexylcyclohexane, isophoronediamine, norbomanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'- diaminodi cyclohexylethane, 4,4'-diaminodicyclohexylpropane, 2,2-bis(4- aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-l-(4- aminocyclohexyl)propane, 1,3- and l,4-bis(aminomethyl)cyclohexane, and l-cyclohexyl-3,4- dimino-cyelohexane. As exemplary 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.

[0064] Suitable amine-epoxide adducts include, for example, reaction products of diamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, m- xylylenediamine and/or bis(aminomethyl)cyclohexane with terminal epoxides such as, polyglycidyl ethers of polyhydric phenols listed above. [0065] Preferably, amine curing agents used with the formulations of the invention are bis(para-aminocyclohexyl)methane (PACM), di ethylene triamine (DETA), and 4,4'- methylenedianiline (MDA). Stoichiometry ratios of amine to epoxy groups of the coating, adhesive, sealant, film, elastomer, casting, foam, and composite compositions of the invention 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.

[0066] Solvents may be included in the formulation of the thermosets of the present invention. 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, ethyl ethoxy propionate, tetrahydrofuran, diethyl ether, dimethylsulfoxide, dimethyl formamide, and dimethylacetamide. Mixtures of solvents may also be used.

[0067] Curing may occur at ambient or low temperatures. By 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.

[0068] 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. Examples of suitable 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. Specific examples of such additives are found in Raw Materials Index, published by the National Paint & Coatings Association, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005. Further examples of such additives may be found in U.S. Pat. No. 5,371,148.

[0069] Examples of flattening agents include, but are not limited to, synthetic silica, available from the Davison Chemical Division ofW. R. Grace & Company as SYLOID; polypropylene, available from Hercules Inc., as HERCOFLAT; synthetic silicate, available from J. M. Huber Corporation, as ZEOLEX.

[0070] Examples of 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.

[0071] Where formulated as a coating, 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. Additionally, a primer may be applied first to the substrate followed by application of the coating of the invention.

Alternatively, the coating of the invention can be applied to the substrate first, followed by a topcoat of another or similar material.

[0072] The 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. In some embodiments, the inventive compositions may be applied in the form of paints or lacquers onto any compatible substrate. In certain embodiments, the inventive composition is applied as a single layer. In other embodiments, the composition may be applied as multiple layers as needed.

EXAMPLES

[0073] The non-limiting and non-exhaustive examples that follow are intended to further describe various non-limiting and non-exhaustive embodiments without restricting the scope of the embodiments described in this specification. All quantities given in “percents” are understood to be by weight, unless otherwise indicated. For the purpose of mass to mole conversions, reagents with purity of 99% or higher are considered to be 100% pure. [0074] Although described herein in the context of a coating, those skilled in the art will recognize that the principles of the present invention are equally applicable to adhesives, sealants, films, elastomers, castings, foams, and composites.

[0075] The following materials were used in preparation of the Examples:

POLYISOCYANATE A an aliphatic isocyanate based on hexamethylene diisocyanate (HDI), commercially available from Covestro LLC (Pittsburgh, PA) as DESMODUR H (49.7% NCO);

POLYISOCYANATE B an allophanate-modified polyisocyanate based on hexamethylene diisocyanate (HDI), commercially available from Covestro LLC (Pittsburgh, PA) as DESMODUR XP 2580 (19.3% NCO);

ALLYL ALCOHOL commercially available from Sigma-Aldrich;

CATALYST A dibutyltin dilaurate 95% (DBTDL), one drop is ~ 20-30 mg, commercially available from Sigma-Aldrich;

CATALYST B methyltrioxorhenium(VII), commercially available from Sigma-Aldrich;

OXIDANT A meta-chloroperoxybenzoic acid (mCPBA), commercially available from Sigma- Aldrich;

OXIDANT B hydrogen peroxide, commercially available from VWR International;

OXIDANT C potassium peroxysulfate, commercially available from Sigma-Aldrich as OXONE;

BASE A sodium hydrogen carbonate, commercially available from Alfa Aesar;

BASE B pyrazole, commercially available from Alfa Aesar;

SOLVENT A acetone, commercially available from Alfa Aesar;

SOLVENT B dichloromethane, commercially available from Alfa Aesar;

SOLVENT C ethyl acetate, commercially available from BeanTown Chemical;

CROSSLINKER A para-aminocyclohexyl methane (PACM), commercially available from Evonik;

THIOSULFATE Na2S20s, commercially available from Alfa Aesar;

MgSO ₄ magnesium sulfate, anhydrous, commercially available from Alfa Aesar;

DI water de-ionized water;

MEK methyl ethyl ketone, commercially available from VWR

International; and 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.

[0076] FTIR measurements were made using a THERMO NICOLET 8700 FTIR spectrometer. Spectra acquisitions were based on 64 scans with data spacing of 4.0 cm’ ¹ in the range of 4000-500 cm’ ¹ . NMR measurements were made at 25 °C using a BRUKER AVANCE 400 MHz instrument and processed with TOPSPIN software. All measurements were made using CDCh as solvent. The bulk viscosity of samples was measured using an ARES Rheometer at room temperature. Epoxide equivalent weight (EEW, g/eq) of the epoxy products was determined by epoxy titration according to ASTM D1652-11 (2019). Impact tests were measured according to ASTM D2794-93 (2019) using a BYK-Gardner Heavy Duty Impact Tester Model IG-1120, with a 1.8 kg (4 lb.) mass and 1.27 cm (0.5 inch) diameter round-nose punch. MEK double rubs (MEK DRs) of the cured film was assessed according to ASTM D5402-19. Coatings that passed 400 double rubs without mar were considered fully cured. The film thickness was measured with a BYKO-TEST 8500 coating thickness gauge. Konig pendulum hardness and pencil hardness were measured according to ASTM D4366-16 (2021) and ASTM D3363-20, respectively. The adhesion of coatings on steel substrate was evaluated according to crosshatch adhesion test, ASTM D3359-17.

Ex. 1 - Synthesis of HDI-GC resin (FIG. 1)

Step one: Synthesis of HDI allyl carbamate

[0077] A mixture containing ALLYL ALCOHOL (14.684 g, 0.2528 mol) and two drops of CATALYST A in 100 mL dry SOLVENT B was stirred at room temperature. POLYISOCYANATE A (20.22 g, 0.119 mol) was added dropwise. After completion of the dropwise addition, the reaction mixture was stirred at room temperature overnight. Infrared spectroscopic analysis was performed to determine the reaction completion by monitoring the disappearance of the isocyanate peak at 2275 cm’ ¹ . The white powder HDI-allyl carbamate was obtained at 96.8% yield; the raw product was used for the next step without purification.

Ex. 2 (Comparative)

Step Two: Epoxidation using OXIDANT A

[0078] The HDI allyl carbamate made in Ex. 1 (14.2 g 50 mmol) was dissolved in SOLVENT B (100 mL) and OXIDANT A (50 g -70% mixture, 200 mmol) was added at once. The reaction mixture was stirred for 48 hours and washed with saturated BASE A with THIOSULFATE (2 g). The organic layer was dried using MgSO4 and concentrated to yield a yellow powder. The carbon-carbon double bond conversion was about 96% (analyzed by ¹³ C NMR spectroscopy, FIG. 2) and the yield was about 90%. Flash chromatography was needed to obtain pure resin.

Ex. 3 (Comparative)

Step Two: Epoxidation using OXIDANT B

[0079] The HDI allyl carbamate synthesized in Ex. 1 (2.8417 g, 10 mmol) was dissolved in ethyl acetate (10 mL) in a 50 mL three-neck, round bottom flask. CATALYST B (24 mg, 0.1 mmol) and BASE B (32.04 mg and 0.5 mmol) were added into flask. Next, OXIDANT C aqueous solution (35%, 3g) was added. The reaction mixture was stirred for 60 additional hours. The carbon-carbon double bond conversion was about 30% (analyzed by ¹³ C NMR spectroscopy, FIG. 3). The yield was not measured.

Ex. 4 - (Inventive)

Step 2: Epoxidation using OXIDANT C

[0080] To a 250 mL three-neck, round bottom flask, was added the HDI allyl carbamate from Ex. 1 (1.41 g, 5 mmol), SOLVENT A (30 mL), BASE A (4 g). OXIDANT C solution (14 g in 80 mL DI water) was added dropwise via an addition funnel over about five hours. After completion of the addition, the reaction solution was stirred at room temperature for another hour. The reaction mixture was liquid-liquid extracted with SOLVENT C (3 x 30 mL). The organic layer was separated and washed with BRINE and evaporated. The conversion was analyzed by ¹³ C NMR, FIG. 4. The conversion was 100% and yield was -83%.

[0081] Table I summarizes the results of the three different epoxidation methods and shows that the method using OXIDANT C results in 100% conversion of double bonds to epoxy groups.

Table I

Ex. 5 - Synthesis of POLYISOCYANATE B-GLYCIDYL CARBAMATE resin (FIG. 5) [0082] A mixture containing ALLYL ALCOHOL (5.473 g, 92.3mmol) and two drops of CATALYST A was stirred at room temperature. POLYISOCYANATE B (20 g, 92.3mmol) was added dropwise. After completion of the dropwise addition, the reaction solution was stirred at room temperature for overnight. Infrared spectroscopic analysis was performed to determine reaction completion by monitoring the disappearance of isocyanate peak at 2275 cm ¹ . The resultant POLYISOCYANATE B-ALLYL CARBAMATE was used for next step without purification.

[0083] The solution of the POLYISOCYANATE B-ALLYL CARBAMATE in SOLVENT A (150 mL) was transferred to a 1000 mL three neck, round bottom flask equipped with a mechanical stirring apparatus. BASE A (32 g) was added at once. A solution of OXIDANT C (120 g/450 mL DI) was added dropwise at a flowrate of 0.5 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 deionized water and BRINE and evaporated. The conversion was analyzed by ¹³ C NMR. The conversion was 100% and yield is close to 100%.

Ex. 6 - Synthesis of POLYISOCYANATE B-GLYCIDYL CARBAMATE RESIN Step one: Synthesis of allyl carbamate resin

[0084] In a 1000 mL three-neck flask equipped with a mechanical stirring apparatus and a 250 mL addition funnel, ALLYL ALCOHOL (59.21 g. 1.02 mol) and three drops of CATALYST A were added. POLYISOCYANATE B (251.10 g, 1 mol) was added into the addition funnel and SOLVENT B (30 mL) was used to transfer all the POLYISOCYANATE B into the addition funnel. Then, the isocyanate was added dropwise into the flask. After finishing the addition (about 10 mL SOLVENT B was added into the addition funnel to wash all POLYISOCYANATE B into the reaction flask), the reaction mixture kept stirring until all isocyanate groups were consumed, which was determined by FTIR. After the reaction was finished, SOLVENT B was removed by vacuum. The residue was used for epoxidation without further purification.

[0085] ’H NMR (400 MHz, CDC13) 6 8.64 - 8.36 (m), 5.98 - 5.64 (m), 5.29 - 5.21 (m), 5.16 (dd, J = 12.9, 5.1 Hz), 5.06 (d, J = 10.3 Hz), 4.37 (t, J = 31.0 Hz), 4.13 - 3.91 (m), 3.81 - 3.67 (m), 3.66 - 3.51 (m), 3.24 - 3.09 (m), 3.09 (s), 1.66 - 1.48 (m), 1.48 - 1.33 (m), 1.31 - 1.10 (m), 0.96 - 0.68 (m). [0086] ¹³ C NMR (101 MHz, CDC13) 6 156.30, 156.24, 154.39, 148.90, 133.08, 117.18,

68.07, 66.60, 66.31, 65.14, 43.46, 42.68, 40.71, 40.25, 30.49, 29.72, 29.66, 29.37, 28.92, 28.14, 27.94, 27.57, 26.41, 26.23, 26.16, 26.11, 22.10, 21.88, 19.02, 13.85, 13.53, 10.34. FIG. 6 shows the NMR spectrum of the POLYISOCYANATE B- ALLYL CARBAMATE.

[0087] ATR-FTIR (neat) 3333, 2932, 2859, 1683, 1527, 1461, 1404, 1361, 1239, 1181, 1136, 1032, 991, 928, 777, 765, 733 cm ⁴

Step two: Epoxidation of allyl carbamate resin

[0088] To a 12 L three-neck, round bottom flask equipped a mechanical stirring apparatus, the POLYISOCYANATE B-ALLYL CARBAMATE made in step one, SOLVENT A (1.5L), and BASE A (503.65g, 6 mol) were added. OXIDANT C (1223g, 4 mol in about 4.8L DI water) was added into the reaction mixture by a piston pump at an addition rate from 2 mL/min to 4 mL/min over about 72 hours. After finishing the addition of the OXIDANT C solution, the reaction mixture was kept stirring for another hour. Ethyl acetate (1.5L) was added into flask. The reaction mixture was kept stirring for additional ten minutes to let the product dissolve in ethyl acetate. After the dissolution was complete, the clear solution was transferred to a separate funnel. The water layer was washed with ethyl acetate (200 mL) once. The combined ethyl acetate was washed using BRINE (3 x 225 mL). The light yellow and clear ethyl acetate solution was dried by magnesium sulfate. After removing the solvent by rotary evaporator and vacuum oven, 290 g (100% yield) resin was obtained. The double bond conversion was 100% analyzed by ¹³ C NMR spectroscopy.

[0089] ’H NMR (400 MHz, CDCh) 5 8.55 - 8.26 (m), 5.46 (t, J = 19.3 Hz), 4.23 (ddd, J = 13.5, 9.1, 3.0 Hz), 4.01 - 3.93 (m), 3.74 - 3.56 (m), 3.51 (s), 3.11 - 3.00 (m), 2.94 (dt, J = 12.9, 4.7 Hz), 2.67 - 2.54 (m), 2.41 (dd, J = 4.6, 2.5 Hz), 1.60 - 1.37 (m), 1.37 - 1.25 (m), 1.25 - 1.07 (m), 0.75 (ddd, J = 23.7, 13.3, 7.2 Hz).

[0090] ¹³ C NMR (101 MHz, CDCh) 8 156.09, 154.30, 148.88, 67.98, 66.22, 65.15,

64.98, 49.67, 49.54, 49.49, 44.24, 43.36, 42.55, 40.68, 40.63, 40.15, 30.60, 30.39, 29.52, 29.46, 29.26, 28.81, 28.03, 27.85, 27.45, 26.30, 26.13, 26.05, 26.02, 22.00, 21.78, 18.93, 13.75, 13.43, 10.25. FIG. 6 shows the ¹³ C NMR spectrum of the POLYISOCYANATE B- GLYCIDYL CARBAMATE RESIN. [0091] ATR-FTIR (neat) 3334, 2922, 2860, 1682,1526, 1462, 1404, 1372, 1237, 1181, 1142, 1022, 908, 858, 765, 729cm . FIG. 7 shows the ATR-FTIR spectrum of the POLYISOCYANATE B-GLYCIDYL CARBAMATE RESIN.

Coating preparation and evaluation

[0092] The POLYISOCYANATE B-GLYCIDYL CARBAMATE RESIN from Ex. 6 was mixed with the CROSSLINKER A at the ratios as noted in Table II without using any solvent. The coating formulations were applied on to iron phosphate pretreated 22 -gauge steel test panels purchased from Q-Lab. Coating application was made using a drawdown bar for a final dry film thickness of approximately 80pm. Coated panels were cured at room temperature or placed in an oven at 80 °C. The results of the coating evaluation are shown in Table II.

Table II

RT: room temperature

HT: 80 °C for 45 minutes

Coating preparation and evaluation using self-crosslinking

[0093] POLYISOCYANATE B-GLYCIDYL CARBAMATE RESIN from Ex. 6 was applied on to iron phosphate pretreated 22-gauge steel test panels purchased from Q-Lab. Coating application was made using a drawdown bar for a final dry film thickness of approximately 70pm. Coated panels were placed in an oven at 150 °C for one-hour and the results are given in Table III.

Table III

[0094] This specification has been written with reference to various non-limiting and non-exhaustive embodiments. However, it will be recognized by persons having ordinary skill in the art that various substitutions, modifications, or combinations of any of the disclosed embodiments (or portions thereof) may be made within the scope of this specification. Thus, it is contemplated and understood that this specification supports additional embodiments not expressly set forth herein. Such embodiments may be obtained, for example, by combining, modifying, or reorganizing any of the disclosed steps, components, elements, features, aspects, characteristics, limitations, and the like, of the various non-limiting embodiments described in this specification. In this manner, Applicant reserves the right to amend the claims during prosecution to add features as variously described in this specification, and such amendments comply with the requirements of 35 U.S.C. §112(a), and 35 U.S. C. §132(a).

[0095] Various aspects of the subject matter described herein are set out in the following numbered clauses:

Clause 1. A glycidyl carbamate-functional composition comprising a reaction product of an allyl carbamate composition with a ketone, water, a base, and an aqueous solution of an oxidant, wherein the allyl carbamate composition comprises a reaction product of a polyisocyanate, allyl alcohol, and optionally a catalyst.

[0096] Clause 2. The glycidyl carbamate-functional composition according to Clause 1, wherein the reaction occurs at a temperature of from 2 °C to 90 °C.

[0097] Clause 3. The glycidyl carbamate-functional composition according to one of Clauses 1 and 2, wherein the reaction occurs at a temperature of from 18 °C to 25 °C.

[0098] Clause 4. The glycidyl carbamate-functional composition according to any one of Clauses 1 to 3, wherein the isocyanate is selected from the group consisting of 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-l,3-diisocyanate, cyclohexane-l,4-diisocyanate, l-isocyanato-2-isocyanato-methyl cyclopentane, l-isocyanato-3,3,5-trimethyl-5-isocyanato- methylcyclohexane (IPDI), bis-(4-isocyanatocyclohexyl)methane (HnMDI), 1,3- bis(isocyanatomethyl)-cyclohexane, l,4-bis(isocyanatomethyl)-cyclohexane, bis-(4- isocyanato-3-methyl-cyclohexyl)-methane, a,a,a',a'-tetramethyl-l,3-xylene diisocyanate, a,a,a',a'-tetramethy-l ,4-xylene diisocyanate, 1 -isocyanato-1 -methyl-4(3)-isocyanato-methyl cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentane diisocyanate (PDI) - biobased), isomers of any of these, and mixtures of any of these.

[0099] Clause 5. The glycidyl carbamate-functional composition according to any one of Clauses 1 to 4, wherein the reaction occurs in the presence of a solvent selected from the group consisting of 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, and mixtures of any of these. [0100] Clause 6. The glycidyl carbamate-functional composition according to any one of Clauses 1 to 5, wherein the catalyst is selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, and l,4-diazabicyclo[2.2.2]octane (DABCO), and mixtures of any of these.

[0101] Clause 7. The glycidyl carbamate-functional composition according to any one of Clauses 1 to 6, wherein the base is selected from the group consisting of sodium hydrogen carbonate (sodium bicarbonate), sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide, and mixtures of any of these.

[0102] Clause 8. The glycidyl carbamate-functional composition according to any one of Clauses 1 to 7, 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.

[0103] Clause 9. A process for producing a crosslinked thermoset polymer, the process comprising curing the glycidyl carbamate-functional composition according to any one of Clauses 1 to 8 with a curing agent reactive with epoxy-functional groups.

[0104] Clause 10. The process according to Clause 9, wherein the curing agent comprises an amine.

[0105] Clause 11. A process of self-crosslinking the glycidyl carbamate-functional composition according to any one of Clauses 1 to 8 comprising heating the composition to a temperature of from 30 °C to 100 °C.

[0106] Clause 12. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the glycidyl carbamate-functional composition according to any one of Clauses 1 to 8.

[0107] Clause 13. A substrate having applied thereto a coating comprising the glycidyl carbamate-functional composition according to any one of Clauses 1 to 8.

[0108] Clause 14. The substrate according to Clause 13, wherein the substrate is selected from the group consisting of metals, plastics, ceramics, glass, natural materials, and concrete.

[0109] Clause 15. The substrate according to one of Clauses 13 and 14, wherein the coating is cured.

[0110] Clause 16. A process for producing a glycidyl carbamate-functional composition, the process comprising reacting a polyisocyanate with allyl alcohol, optionally in the presence of a catalyst, to produce an allyl carbamate composition; and combining the allyl carbamate composition with a ketone, water, a base, and an aqueous solution of an oxidant to produce the glycidyl carbamate-functional composition.

[oni] Clause 17. The process according to Clause 16, wherein the process occurs at a temperature of from 2 °C to 90 °C.

[0112] Clause 18. The process according to one of Clauses 16 and 17, wherein the process occurs at a temperature of from 18 °C to 25 °C.

[0113] Clause 19. The process according to any one of Clauses 16 to 18, wherein the isocyanate is selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-l,6-hexamethylene diisocyanate, 2,4,4- trimethyl-l,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-

1.3-diisocyanate, cyclohexane-l,4-diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanato- methylcyclohexane (IPDI), bis-(4-isocyanatocyclohexyl)methane (HnMDI), 1,3- bis(isocyanatomethyl)-cyclohexane, l,4-bis(isocyanatomethyl)-cyclohexane, bis-(4- isocyanato-3-methyl-cyclohexyl)-methane, a,a,a',a'-tetramethyl-l,3-xylene diisocyanate, a,a,a',a'-tetramethy-l ,4-xylene diisocyanate, 1 -isocyanato-1 -methyl-4(3)-isocyanato-methyl cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentane diisocyanate (PDI) - biobased), isomers of any of these, and mixtures of any of these.

[0114] Clause 20. The process according to any one of Clauses 16 to 19, wherein the step of reacting occurs in the presence of a solvent selected from the group consisting of 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, and mixtures of any of these.

[0115] Clause 21. The process according to any one of Clauses 16 to 20, wherein the catalyst is selected from the group consisting of dibutyl tin dilaurate, dibutyl tin diacetate, and

1.4-diazabicyclo[2.2.2]octane (DABCO), and mixtures of any of these.

[0116] Clause 22. The process according to any one of Clauses 16 to 21, wherein the base is selected from the group consisting of sodium hydrogen carbonate (sodium bicarbonate), sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide, and mixtures of any of these.

[0117] Clause 23. The process according to any one of Clauses 16 to 22, 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.

[0118] Clause 24. A process for producing a crosslinked thermoset polymer, the process comprising curing the glycidyl carbamate-functional composition according to any one of Clauses 16 to 23 with a curing agent reactive with epoxy-functional groups.

[0119] Clause 25. The process according to Clause 24, wherein the curing agent comprises an amine selected from the group consisting of bis(para-aminocyclohexyl)methane (PACM), di ethylene triamine (DETA), and 4,4'-methylene dianiline (MDA).

[0120] Clause 26. A process of self-crosslinking the glycidyl carbamate-functional composition produced according to any one of Clauses 16 to 23, the process comprising heating the composition to a temperature of from 30 °C to 100 °C.

[0121] Clause 27. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the glycidyl carbamate-functional composition produced according to the process of any one of Clauses 16 to 23.