Urethane monomers; curable compositions; and acid-reinforced urethane polymers thereof

Abstract

Disclosed herein are urethane monomers, acidic monomer, monovinyl multiurethane monomers, monourethane multivinyl monomers, and oligomeric clustered urethanes; curable compositions thereof; and acid-reinforced urethane polymers.

Description

CU2025-112-PCT (RGC0035PCT)URETHANE MONOMERS; CURABLE COMPOSITIONS; AND ACID-REINFORCED URETHANE POLYMERS THEREOFCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of U. S. Provisional Application Serial Number 63 / 769,301, filed March 10, 2025, which is incorporated herein by reference in its entirety for all purposes.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH & DEVELOPMENT

[0002] This invention was made with government support under Grants No.R21DE032797 and R41DE033937 awarded by National Institutes of Health, National Institute of Dental and Craniofacial Research (NIH / NIDCR). The government has certain rights in the invention.BACKGROUND

[0003] There is a significant need for strong and tough photocurable polymers in the biomedical field as well as in diverse industrial applications, including 3D printing, coatings, adhesives and broader uses. There is a further need for cost-effective routes for monomers used to prepare such polymers.

[0004] The acid-urethane (meth) acrylate formulations prepared from acrylic or methacrylic acid as a reactive diluent for urethane-based materials can provide high-performance materials. Urethane-based materials where the urethane groups are separated from each other by one to three carbon atoms, referred to as “clustered” urethane groups, produce very effectively reinforced copolymer networks when these urethane materials are coordinated with suitable acid-functionalized comonomers. However, acrylic and methacrylic acid exhibit volatility and odor issues. Thus, there remains a need for additional advancement with clustered urethane monomers as well as new acid-functional reinforcing comonomers that offer lower polymerization shrinkage as well as being nonvolatile with low odor or no odor in the monomeric state.CU2025-112-PCT (RGC0035PCT)BRIEF SUMMARY

[0005] In an aspect a urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; and wherein the urethane (meth)acrylate monomer comprises at least one of the following groups:O OOwherein each occurrence of X independently is hydrogen or methyl: and each occurrence of R1is independently hydrogen or, together with the O, an ether, ester, carbonate, or urethane (carbamate) group.

[0006] In a further aspect, a curable composition comprises an acidic or latent acidic comonomer that is mono-2-(methacryloyloxy)ethyl succinate (MMES), mono-2-(methacryloyloxy)ethyl maleate (MMEM), mono-2-(acryloyloxy)ethyl itaconate (MAEI), acrylated nadic or carbic anhydride obtained from ring-opened cyclic anhydride with 2-hydroxyethyl (meth)acrylate, a ring-opened cyclic anhydride with a hydroxy functionalized (meth)acrylate, or a combination thereof; and a urethane (meth)acrylate monomer comprising 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; wherein a molar ratio of urethane groups in the urethaneCU2025-112-PCT (RGC0035PCT)(meth) acrylate monomer to carboxylic acid and carboxylic acid anhydride groups in the acidic or latent acidic comonomer is 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1.

[0007] In an aspect, a curable composition comprises a monovinyl multiurethane monomer comprising a single vinyl group and 2 to 12 urethane groups wherein each of at least two urethane groups is separated from at least one other urethane group by at most three carbon atoms; a urethane (meth)acrylate monomer; and optionally further comprising an acidic monomer.

[0008] In yet another aspect, a monourethane multivinyl monomer comprises one urethane group and 2 to 6 (meth)acrylate groups; wherein the monourethane multivinyl monomer has a molecular weight of greater than or equal to 150 grams / mole to less than or equal to 1,500 grams / mole.

[0009] In a further aspect, an oligomeric clustered urethane comprises: a) the reaction product of monourethane diol produced from the ring-opening of ethylene carbonate with ethanolamine in reaction with a diisocyanate to give oligomeric clustered urethane; or b) a diurethane diol from ethylene carbonate (EC) plus ethylenediamine can be used to construct clustered tetraurethane segments.DETAILED DESCRIPTION

[0010] Disclosed herein are new approaches to acid-reinforced urethane polymers, including high-performance acid-reinforced urethane polymers. Further disclosed herein are novel urethane monomers; new cost-effective routes to urethane monomers; novel acidic monomers for use with urethane comonomers, which are low volatile and odor free; monovinyl multiurethane monomers; monourethane multivinyl monomers; and oligomeric clustered urethanes. Also disclosed are curable compositions comprising the novel monomers, comonomers, and / or oligomeric clustered urethanes, as well as the cured material obtained from curing such compositions.

[0011] As used herein, the term “(meth)acrylate” means “acrylate” or “methacrylate.”CU2025-112-PCT (RGC0035PCT)Urethane monomers from (2-oxo-l,3-dioxolan-4-yl)methyl methacrylate (“GMEC”) and (2-oxo- 1,3-dioxolan-4-yl)methyl prop-2-enoate:

[0012] In one aspect, are novel urethane monomers prepared from (2-oxo-l,3-dioxolan-4-yl)methyl methacrylate (“GMEC”; CAS# 13818-44-5) or (2-oxo-l,3-dioxolan-4-yl)methyl prop-2-enoate (CAS# 7528-90-7). Compared to the use of ethylene carbonate to prepare urethane monomers. GMEC and the acrylate analog allow for the synthesis of new urethane structures including clustered urethanes (< 3 atoms between urethane groups) to be prepared without reliance on isocyanatoethyl methacrylate (IEM) and related expensive materials. The use of GMEC is therefore cost effective. Additionally, GMEC allows for the synthesis of unique structures that cannot be accessed via isocyanate (meth)acrylates.

[0013] In an aspect, a urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; and wherein the urethane (meth)acrylate monomer comprises at least one of the following groups:OOwherein each occurrence of X independently is hydrogen or methyl; and each occurrence of R1is independently hydrogen or, together with the O, an ether, ester, carbonate, or urethane (carbamate) group.CU2025-112-PCT (RGC0035PCT)

[0014] In a further aspect, the urethane (meth)acrylate monomer comprises 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 urethane groups and comprises 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 (meth)acrylate groups.

[0015] In a further aspect, the urethane (meth)acrylate monomer wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms.

[0016] In a further aspect, the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5.000 grams / mole. Within this limit, the maximum molecular weight of the urethane (meth)acrylate monomer can be 4,000 grams / mole, or 3,000 grams / mole, or 2,000 grams / mole, or 1,000 grams / mole, or 500 grams / mole, or 150 grams / mole.

[0017] Scheme 1. illustrates an example for the preparation of trihydroxy-diurethane dimethacrylate (THDUDMA) prepared from two equivalents of GMEC and l,3-diamino-2-propanol. Characterization of the product shows the reaction provides a 3-carbon spacer between clustered urethanes along with an alternating hydroxy-urethane configuration. This monomer can be formulated with acidic comonomers such as (meth)acrylic acid, or one of the novel acidic comonomers described herein, to obtain crosslinked polymers with very high strength, stiffness and toughness. The THDUDMA can also be further reacted with varied isocyanates to produce the pentaurethane dimethacrylate (PUDMA) that places additional clustered urethane linkages as side-chains. A related tetraurethane dimethacrylate (TUDMA) can be made with the reaction of two equivalents of GMEC with a diamine followed by mono-isocyanates or alternatively by reaction of GMEC with monoamines or hydroxyamines, and then a diisocyanate.CU2025-112-PCT (RGC0035PCT)

[0018] Scheme 1. illustrates one approach to including an aromatic group in the urethane side chain. In an aspect, an aliphatic or benzyl isocyanate is used rather than phenyl isocyanate as urethane substituted directly onto an aromatic ring does not respond well to the acidic comonomer reinforcement.

[0019] Suitable diamines include those of the structure H2N-R2-NH2 wherein R2is alkyl (linear, branched or cyclic), alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or -alkylarylalkyl-. Alkyl groups include C1-40, specifically C2-20, and more specifically C3-10. Examples of suitable aliphatic diamines include methylene diamine dihydrochloride; 1,2-ethylene diamine; 1,2-diaminopropane; 1,3 -diaminopropane; 2,2-dimethyl-CU2025-112-PCT (RGC0035PCT)1,3-diaminopropane; 2,4,4-trimethylhexyl diamine; dimer diamine (C36 cycloaliphatic diamine); and the like. Alkyl groups with 1 or more internal heteroatoms can include 1, 2, 3, or more heteroatoms such as O, S. and N. Examples of suitable diamines with alkyl having 1 or more internal heteroatoms include diethylenetriamine; 2-(2-aminoethoxy)ethylamine; poly(ethylene glycol) diamine, e.g., having 1 to 10 ethylene glycol repeat units; and the like. A diamine having an alkyl with 1 or more pendent groups includes, for example. l,3-diamino-2-propanol.Examples of suitable aryl and alkylarylalkyl diamines include those where the aryl is phenyl, for example, o, m, or p-phenylene diamine; o, m, or p-xylylenediamine; and the like.

[0020] Suitable mono-isocyanates include those of the structure R3-NCO where R3is an alkyl, aryl, or -alkylaryl where the isocyanate group is attached through the alkyl. Alkyl groups include linear, branched, or cyclic alkyl groups having a C1-40, specifically C2-20, and more specifically C3-10 alkyl. The aryl can be phenyl. The alkylaryl can be -Ci-isalkyl-aryl, specifically Ci-salkyl-aryl where the aryl is phenyl.

[0021] Suitable monoamines include those of the structure R4-NH2 where R4is an alkyl, aryl, or -alkylaryl where the amine group is attached through the alkyl. The alkyl groups include linear, branched, or cyclic alkyl groups having a C1-40, specifically C2-20, and more specifically C3-10 alkyl. The aryl can be phenyl. The alkylaryl can be -Ci-isalkyl-aryl, specifically Ci-salkyl-aryl where the aryl is phenyl. Examples of monoamines include benzyl amine (with or without substitution), phenethylamine, phenoxyethylamine, and the like.

[0022] Suitable hydroxy amines include those of the structure HO-R5-NH2 where R3is alkyl (linear, branched or cyclic), alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or -alkylarylalkyl-. Examples of hydroxy amines include ethanolamine; N-(2-hydroxyethyl)ethylenediamine; 2-amino-l,3-propanediol; l-amino-2,3-propanediol; tris(hydroxymethyl)aminomethane; 2-amino-l-phenylethanol; and the like.

[0023] Suitable diisocyanate include those of the structure OCN-R6-NCO wherein R6is alkyl (linear, branched or cyclic), alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or -alkylarylalkyl-. Alkyl groups include C1-40, specifically C2-20, and more specifically C3-10. Alkyl groups with 1 or more internal heteroatoms can include 1, 2, 3, or more heteroatoms such as O, S, and N. The pendent groups for the alkyl with 1 or more pendent groups can include alkyl, aryl, or -alkylaryl.CU2025-112-PCT (RGC0035PCT)

[0024] Examples of suitable diisocyanates include CAS 38661-72-2 1,3-bis(methylisocyanate)-cyclohexane; CAS 10347-54-3 l,4-bis(methylisocyanate)-cyclohexane; CAS 2556-36-7 1, 4-cy cl ohexane diisocyanate; CAS 134190-37-7 diethyldiisocyanatobenzene; CAS 4128-73-84,4'-diisocyanatodiphenyl ether; CAS 75790-87-3 2,4'-diisocyanatodiphenyl sulfide; CAS 91-93-03,3'-dimethoxybenzidine-4,4'-diisocyanate; CAS 91-97-43,3'-Dimethyl-4,4'-diphenylene diisocyanate; CAS 139-25-33,3'-dimethyldiphenylmethane-4,4'-diisocyanate; CAS 822-06-0 hexamethylene- 1,6-diisocyanate; CAS 4098-71-9 isophorone diisocyanate; CAS 75790-84-04-methyldiphenylmethane-3,4-diisocyanate; CAS 5124-30-1 l,l-methylenebis(4-isocyanatocy cl ohexane); CAS 101-68-8 methylene bis(phenylisocyanate) (MDI); CAS 3173-72-6 1,5-naphthalene diisocyanate; CAS 123-61-5 1,3-phenylene diisocyanate; CAS 104-49-4 1,4-phenylene diisocyanate; CAS 26471-62-52,4- / 2,6-Toluene diisocyanate mixture (TDI); CAS 16938-22-02, 2, 4-trimethylhexam ethylene diisocyanate; CAS 15646-96-5 2,4,4-trimethylhexamethylene diisocyanate; and CAS 3634-83-1 m-xylylene diisocyanate. Particular diisocyanates include 1.3-bis(methylisocyanate)-cy cl ohexane; l,4-bis(methylisocyanate)-cyclohexane; 1, 4-cy cl ohexane diisocyanate; 3,3'-Dimethyl-4,4'-diphenylene diisocyanate; hexamethylene- 1,6-diisocyanate; isophorone diisocyanate; l,l-methylenebis(4-isocyanatocy cl ohexane); 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; and m-xylylene diisocyanate.

[0025] A variety of hydroxy-functionalized urethane monomers available from reaction with GMEC, or its acrylate analog, with amines can provide both mono-, di- and multi-vinyl monomers that are water soluble. Several of these hydroxy-functionalized urethane monomers have been used in water-based formulations with acrylic acid, or related comonomers, and an ion-leachable filler to obtain resin-modified glass ionomer cements with good properties. The GMEC-based urethane monomers have been combined with acidic comonomers and particulate glass fillers to create direct placement dental composite materials.

[0026] The GMEC, or its acrylate analog, starting material can also be used to prepare branched urethane monomers in a variety of manners. In a first example, GMEC is ring opened with an amine (H2N-R4; route A Scheme 2A.) to give a mixture of hydroxy-urethane methacrylate isomers that can be further reacted with a diisocyanate (OCN-R6-NCO) to give two urethane groups integrated into the crosslinker segment as well as two additional urethanes included as pendant groups. Each of the branched urethanes are considered clustered with theirCU2025-112-PCT (RGC0035PCT)neighboring urethanes. This clustered urethane configuration promotes unusually high mechanical strength and modulus in copolymers prepared with certain acidic comonomers. Alternatively, the same general tetraurethane dimethacrylate can be synthesized via route B (Scheme 2B.) that offers more options in the in the core diurethane structure since there are many more options of diamines (H2N-R2-NH2) compared with diisocyanates. The other consideration is that there are readily available diamines with two or three atoms between the amines that render clustered urethanes in the linear core structure in addition to clustering extending to the pendant urethanes.CU2025-112-PCT (RGC0035PCT)+ H2N-R4OCN- R6— NCOCU2025-112-PCT (RGC0035PCT)Scheme 2B.+ H2N- R2— NH2- ►wherein X, R2, R3, R4, and R6have been previously defined.

[0027] Use of the GMEC starting material, or its acrylate analog, allows for the formation of monovinyl multi-urethanes based on the simple ring-opening addition of an amine, which generates a mix of hydroxy-urethane methacrylate isomer intermediates than can be converted to clustered diurethane monomers with isocyanate addition in the second step (Scheme 3.). Monomers like these provide an option to combine with crosslinkable urethanes to reduce the overall covalent network density of polymers without reducing the urethane content. The coordination of these urethane monomers with acid-functionalized comonomers has the potential to significantly enhance the mechanical properties of these polymers. A separate approach using ethylene carbonate reacted with an amine produces a hydroxy-functionalized mono-urethane that then can be further reacted with isocyanatoethyl (meth)acrylate to yield a linear diurethane mono(meth)acrylate analog of the branched mono-vinyl urethane structures (Scheme 4.).CU2025-112-PCT (RGC0035PCT)Scheme 3.+ H2N-R4wherein X, R3, and R4have been previously defined.CU2025-112-PCT (RGC0035PCT)Scheme 4.OX N R7Hwherein X is hydrogen or methyl; and R7is alkyl (linear, branched or cyclic), alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or alkylarylalkyl.

[0028] Through a similar approach, other hydroxylated amines have been used with GMEC. or its acrylate analog, to make additional clustered multi-urethane monomethacrylates (Scheme 5.). The hydroxylated urethane methacrylate intermediate structures are interesting in their own right based on their compatibility with water and the hydrophilicity they introduce as alternatives to 2-hydroxyethyl (meth)acrylate and other related water soluble (meth)acrylate monomers.CU2025-112-PCT (RGC0035PCT)R3— NCOwherein X and R3have been previously defined.

[0029] Another group of crosslinkable urethane monomers is available from the hydroxyurethanes prepared from GMEC, or its acrylate analog, and amines that can then be appended to a triisocyanate core to make clustered hexaurethane trimethacrylate (Scheme 6.).CU2025-112-PCT (RGC0035PCT)Scheme 6.CU2025-112-PCT (RGC0035PCT)wherein X and R4have been previously defined and R8is alkyl, aryl,— N— (CH2)I_8-*, N. *-(H2C)1.8-NH*-(H2C)1. fT Y YN-(CH2)l-8-*O o, or*-(H2C)1.8-N^( ^N-tClWg-*N-(H2C)1.8-N* — (H2C)I.8— N / / N — (CH2)1.8-*o o

[0030] Suitable triisocyanates include CAS 4035-89-6 1,3,5-tris(6-isocyanatohexyl)biuret (HDI biuret); CAS 3779-63-3 l,3,5-tris(6-isocyanatohexyl)-l,3,5-triazinane-2, 4, 6-trione (HDI trimer isocyanate); l,3,5-triazine-2,4,6-triisocyanate; and the like.NCO l,3,5-triazine-2,4,6-triisocyanate0CN(CH2)g<“*“NCOHDI biuretCU2025-112-PCT (RGC0035PCT)0C N H \; C )% - N- — NCOH(CH^— NCOOCN^CHgC)^ C (OH^^NCOoHDI trimer isocyanate

[0031] In an aspect, a composition, specifically a curable composition, comprises the urethane (meth)acrylate monomer derived from GMEC, or its acrylate analog, and an acidic or latent acidic comonomer. Suitable acidic or latent acidic comonomers include acrylic acid, methacrylic acid, itaconic acid, mono-2-(methacryloyloxy)ethyl maleate, 2-carboxy ethyl acrylate, 2-carboxyethyl methacrylate, mono-2-(methacryloyloxy)ethyl succinate, (meth)acrylic anhydride, itaconic anhydride, maleic anhydride, 4-methacryloxy ethyl methacrylate, 1,3 -glycerol dimethacrylate / succinate adduct (CAS Reg. No. 107665-59-8), 1,3-glycerol dimethacrylate / maleate adduct, pyromellitic dianhydride, 4-methacryloxyethyl trimellitic acid, one of the alternate acidic monomers described herein, or a combination thereof. In some aspects, the acidic or latent acidic comonomer comprises acrylic acid or methacrylic acid.

[0032] The curable composition can comprise the urethane (meth)acrylate monomer and the acidic or latent acidic comonomer in amounts such that a molar ratio of urethane groups in the urethane (meth)acrylate monomer to carboxylic acid and carboxylic acid anhydride groups in the acidic or latent acidic comonomer is 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:3 to 1:1, or 1:1.5 to 1:2.5.CU2025-112-PCT (RGC0035PCT)Acidic monomers for use with urethane comonomers:

[0033] Very high-performance polymers can be prepared using noncovalent urethane-acid reinforcement approaches. One approach is to rely on acrylic acid or methacrylic acid as the reactive diluent that raises strength and stiffness as well as toughness when compared with urethane monomers coupled with conventional diluent comonomers. However, acrylic acid and methacrylic acid suffer from issues of volatility and odor, which have limited use of these compounds as a reactive diluent for urethane-based materials. Described herein are acidfunctional reinforcing comonomers that avoid the issues of volatility and which are odor free.

[0034] Described herein are alternate acidic monomers to replace (meth)acrylic acid, the alternate acidic monomers can include the acidic monomer obtained from ring-opened cyclic anhydrides, such as for example itaconate. maleate, nadic, and norbornene derivatives, with hydroxy functionalized (meth)acrylates. Suitable acidic monomers are obtained from ring-opened cyclic anhydrides with 2-hydroxyethyl (meth)acrylate to obtain mono-2-(methacryloyloxy)ethyl succinate (MMES), mono-2-(methacryloyloxy)ethyl maleate (MMEM), mono-2- (acryloyloxy)ethyl itaconate (MAEI) and the acrylated nadic or carbic anhydride.MMEM Nadic I Carbic Acrylate

[0035] Also included are norbornene-related variations.Additional acidic monomer structures are prepared using itaconic anhydride (Scheme 7.).CU2025-112-PCT (RGC0035PCT)Scheme 7.wherein each occurrence of X independently is hydrogen or methyl; and q is 1 to 10, specifically q is 1.

[0036] There are a variety of additional cyclic anhydride structures that can be opened to produce the acid functionalized monomers (See Schemes 8.-11.). The itaconate, maleate, and nadic derivatives with a hydroxy functionalized caprolactone (meth)acrylate are also nonvolatile, odorless acid monomers suitable as alternatives to (meth)acrylic acid (Scheme 8.).CU2025-112-PCT (RGC0035PCT)Scheme 8.CU2025-112-PCT (RGC0035PCT)wherein each occurrence of X independently is hydrogen or methyl; R9is alkyl, specifically C1-3 alkyl; R10is alkyl, specifically C1-3 alkyl; and y is 0 to 10, specifically where y is 0.

[0037] In further aspects, any of the cyclic anhydrides with a C=C (e.g. in Scheme 8) can be reacted with thioglycolic acid to introduce a thioether-linked carboxylic acid prior to opening the anhydride with a hydroxy acrylate or related monomer. This allows a coupled diacid structure that can coordinate with clustered urethane groups within a polymer network. Such a reaction is shown in Scheme 9 with nadic anhydride but the approach can be applied to other anhydrides with carbon-carbon double bonds such as itaconic anhydride, maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride and others.CU2025-112-PCT (RGC0035PCT)Scheme 9.CU2025-112-PCT (RGC0035PCT)Scheme 10.0Owherein each occurrence of X independently is hydrogen or methyl; and p is 1 to 10, specifically p is 1.Scheme 11.CU2025-112-PCT (RGC0035PCT)wherein X is hydrogen or methyl.Monovinyl multiurethane monomers:

[0038] Monovinyl monourethanes can be used to controllably limit the covalent polymer network density of urethane formulations without reducing the urethane content in coordination with acid-reinforced copolymers. Clustered urethane monomers have been successfully copolymerized with acidic comonomers. In view of these positive results, an approach was developed to prepare monovinyl monomers with clustered urethane structures.

[0039] As used herein monovinyl multiurethane monomers are compounds comprising a single vinyl group, specifically (meth) acrylate group, and 2 to 12 urethane groups wherein each of at least two urethane groups is separated from at least one other urethane group by at most three carbon atoms. In a further aspect, the monovinyl multiurethane monomer has a molecular weight less than or equal to 2,000 grams / mole. Within this limit, the maximum molecular weight of the monovinyl multiurethane monomer can be 1,000 grams / mole, or 800 grams / mole, or 700 grams / mole, or 600 grams / mole, or 500 grams / mole, or 250 grams / mole.

[0040] One method to prepare these monovinyl multiurethane monomers uses ethylene carbonate (EC) with an amine followed by isocyanatoethyl methacrylate (IEM) or isocyanatoethyl acrylate (IEA) to form monovinyl linear urethane and another route relies on GMEC. or its acrylate analog, reacted with an amine and then an isocyanate to make linear and branched clustered urethanes, respectively (Scheme 12.).CU2025-112-PCT (RGC0035PCT)Scheme 12.Linear diurethaneBranched diurethane wherein X, R3, and R4have been previously defined. Analogous methods using substituted ethylene carbonate, glutaric anhydride, or substituted glutaric anhydride can be used to prepare the mono vinyl multiurethane monomers.

[0041] In an aspect, a curable composition comprises a monovinyl multiurethane monomer; a urethane (meth)acrylate monomer; and optionally further comprising an acidic monomer as described herein. In an aspect, the urethane (meth) acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole. In a further aspect, the urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; and wherein the urethane (meth)acrylate monomer comprises at least one of the following groups:0 0CU2025-112-PCT (RGC0035PCT)0wherein each occurrence of X independently is hydrogen or methyl; and each occurrence of R1is independently hydrogen or together with the O an ether, ester, carbonate, or urethane (carbamate) group.

[0042] In a further aspect, a cured composition is the cured product of a composition comprising a monovinyl multiurethane monomer; a urethane (meth)acrylate monomer; and optionally further comprising an acidic monomer as described herein.Monourethane multi vinyl monomers:

[0043] Acid- reinforced polycaprolactone (PCL) urethane monomers and low viscosity monourethane di(meth)acrylates can produce high-performance photo and / or thermally curable resins. Disclosed herein are monourethane multivinyl monomers comprising one urethane group and 2 to 6 (meth)acrylate groups; wherein the monourethane multivinyl monomer has a molecular weight of greater than or equal to 150 grams / mole to less than or equal to 1,500 grams / mole. Within this limit, the maximum molecular weight of the monourethane multivinyl monomer can be 250 grams / mole to 1,250 grams / mole, or 500 grams / mole to 1,000 grams / mole, or 600 grams / mole to 900 grams / mole, or 700 grams / mole to 800 grams / mole.

[0044] In an aspect, a crosslinking monomer combines the PCL spacer in a monourethane di(meth)acrylate (PCL-MUDA). This nonlimiting example uses a hydroxy terminated PCL acrylate reacted with isocyanatoethyl acrylate but there are a variety of related structures that can be obtained with other isocyanato (meth)acrylates. This monomer example produces a homopolymer and copolymers with excellent flexibility. With its viscosity of ~65 mPa*s, it can be used as a reactive diluent with other urethanes while keeping the overall urethane concentration high. It also can be used with acidic comonomers to provide very tough polymers with high flexibility and recovery.CU2025-112-PCT (RGC0035PCT)wherein each occurrence of X independently is hydrogen or methyl; and f is 0 to 10; PCL- MUDA = X is hydrogen and f is 2.

[0045] Another option for making monourethane multivinyl monomers is through the use of GMEC, (2-oxo-1,3-dioxolan-4-yl)methyl prop-2-enoate, or ethylene carbonate with hydroxylated amines to first make the alcohol-functionalized urethane and then (meth)acrylating the pendant OH groups. Three examples include the following GMEC-EA; 3-amino-l,2-propanediol-EC; and 2-amino-l,3-propanediol-EC:GMEC-EA3-Amino-1,2-propanediol - EC2-Amino-1,3-propanediol - EC

[0046] In an aspect, a curable composition comprises a monourethane multivinyl monomer.

[0047] In another aspect, a curable composition comprises a monourethane multivinyl monomer and a urethane (meth) acrylate monomer, an acidic monomer, or both a urethaneCU2025-112-PCT (RGC0035PCT)(meth) acrylate monomer and an acidic monomer. In an aspect, the urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole. In a further aspect, the urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; and wherein the urethane (meth)acrylate monomer comprises at least one of the following groups:O OOwherein each occurrence of X independently is hydrogen or methyl; and each occurrence of R1is independently hydrogen or together with the O an ether, ester, carbonate, or urethane (carbamate) group.

[0048] In a further aspect, a cured composition is the cured product of a composition comprising a monourethane multivinyl monomer and optionally further comprising a urethane (meth)acrylate monomer and / or acidic monomer as described herein.Oligomeric clustered urethanes:

[0049] As an alternative to the use of urethane monomers, the clustered urethane approach can be used with oligomeric urethane (meth) acrylates. In one approach to accomplish this, the monourethane diol produced from the ring-opening of ethylene carbonate withCU2025-112-PCT (RGC0035PCT)ethanolamine can be used in reaction with varied diisocyanates to give oligomeric urethanes that incorporate clustered triple urethane segments (Scheme 13.). There are a variety of urethane diol structural options. The ratio of diisocyanate to urethane diol can control the average molecular weight of the oligomer and maintaining an excess of the diisocyanate leaves isocyanate end groups available that can be simply functionalized to reactive (meth)acrylates with 2-hydroxyethyl (meth)acrylate or related compounds.Scheme 13.wherein each occurrence of X independently is hydrogen or methyl; R6is as previously defined; and g is 1 to 500.

[0050] In another aspect, the diurethane diol from ethylene carbonate (EC) plus ethylenediamine can be used to construct clustered tetraurethane segments (Scheme 14.).Ethylene or propylene glycol plus diisocyanate can also provide the paired urethane clusters within oligomers.Scheme 14.CU2025-112-PCT (RGC0035PCT)wherein R2and R6are as previously defined; n is 1 to 500; and m is 1 to 500.

[0051] In a further aspect, a curable composition comprises an oligomeric clustered urethane, and optionally one or more of a urethane monomer, an acidic monomer, a monovinyl multiurethane monomer, and a monourethane multivinyl monomer. In a further aspect is a cured composition thereof.

[0052] Another aspect is a cured composition comprising the product of curing the curable composition as described herein. Methods of curing (meth)acrylate resins, including thermal, photochemical, and electron beam curing methods are known in the art, as are catalysts for such methods. Illustrative curing methods are included in the experimental examples below.

[0053] In an aspect, a curable composition comprises a urethane (meth)acrylate monomer comprising 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole, and has the following structure (I), or (II):wherein each occurrence of X independently is hydrogen or methyl; and j is 1, 2, or 3, specifically 2 or 3; and an acidic or latent acidic comonomer or alternate acidic monomerCU2025-112-PCT (RGC0035PCT)described herein. Within this aspect, the molar ratio of urethane groups in the urethane (meth) acrylate monomer to carboxylic acid and carboxylic acid anhydride groups in the acidic or latent acidic comonomer or alternate acidic monomer is 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1. In a further aspect, the curable composition can optionally further comprise a urethane monomer from (2-oxo-l,3-dioxolan-4-yl)methyl methacrylate (“GMEC”) and (2-oxo-l,3-dioxolan-4-yl)methyl prop-2-enoate as described herein, a monovinyl multiurethane monomer as described herein; a monourethane multivinyl monomer as described herein; an oligomeric clustered urethane as described herein; or a combination thereof.

[0054] Another aspect is a cured composition comprising the product of curing the curable composition as described herein.

[0055] Another aspect is an article comprising the cured composition, including, for example, a dental adhesive, a dental filling, a dental composite, a dental restorative material, a dental prosthetic device, and the like.

[0056] The monomers and curable compositions described herein find use as adhesives, coatings, films, etc.

[0057] The monomers and curable compositions may further be combined with a filler. Suitable fillers include silicate glass, barium glass, ytterbium glass, ytterbium fluoride, or a combination thereof, as well as any of the above fillers surface treated with (meth)acrylate-treated silanes. The curable composition can comprise 5 to 900 parts by weight of the filler per 100 parts by weight total of the monomer.

[0058] The new acid monomers described herein can serve as an alternative to (meth)acrylic acid and used, for example in 3D printing applications.

[0059] The invention is further illustrated by the following non-limiting examples.EXAMPLESExample 1.

[0060] Table 1 presents properties for cured compositions as a function of urethane monomer, acidic monomer, and curing type. Properties are percent conversion of double bonds (determined by near infrared spectroscopy), flexural strength (in units of megapascals, determined at 23 °C according to ISO 4049:2019), flexural modulus (in units of gigapascals, determined at 23 °C according to ISO 4049:2019), and toughness (in units of megapascals,CU2025-112-PCT (RGC0035PCT)determined at 23 °C according to ISO 4049:2019 based on the area under the flexural stressstrain curve).Table 1.FlexuralUrethane Acidic Conversion, Modulus, Toughness,Cure strength,monomer1monomer2 3% GPa MPa MPa6.66MAA thermal 89.0 (1.6) 149.4 (16.5) 2.0 (1.6)(0.66)6.74AA thermal 97.1 (0.6) 231.8 (35.6) 6.2 (3.1)(0.25) THDUDMA5.10ambient 95.0 (0.7) 221.4 (24.6) 21.1 (6.5)(0.56)AA (2x)6.71thermal 98.0 (1.2) 211.4 (44.0) - (0.89)TAEA- 7.42AA (4.8) ambient - 259.5 (28.2) 15.1 (11.8) GMEC (0.78)BzA- 4.57AA ambient - 198.1 (13.0) 15.0 (9.7) GMEC-XDI (0.18)DAP- 6.05AA thermal - 228.8 (27.7) 6.4 (2.5)GMEC (0.18)'Urethane monomer description or reactant designation• THDUDMA: GMEC + 1.3-diamino-2-propanol• TAEA: tris(2-aminoethyl)amine• DAP: Diaminopropane• BzA: Benzyl Amine• XDI: Xylylene Diisocyanate2Urethane to acid functionality is 1:1 unless specified otherwise. MAA = methacrylic acid; AA = acrylic acid.’Thermal cure indicates an ambient photopolymerization followed by a thermally assisted postcure at 80 °C for 1 hour with continued irradiation. Ambient cure indicates photocure only.DAP-GMECCU2025-112-PCT (RGC0035PCT)TAEA-GMEC

[0061] Table 2. presents properties for cured compositions for thermal cure unless otherwise indicated.Table 2.Flexural StrengthModulus (GPa) Toughness (MJ / m3)(M Pa)Avg. Std. Dev. Avg. Std. Dev. Avg. Std. Dev. UDMA + Nadic-HEA 3.96 0.14 159.29 9.56 8.02 3.29 UDMA + PCL- 1.22 0.13 63.89 4.46 11.53 2.33 ItaconateMUDMA + DDSA- 2.80 0.17 108.71 10.07 6.43 3.80 HEA (1:1)MUDMA + DDSA- 3.28 0.22 121.77 28.60 3.62 2.05 HEA (2:1)MUDA + Nadic-HEA 5.18 0.21 180.54 12.71 4.10 0.94 MUDA + HEA- 3.55 0.47 146.42 24.10 6.06 3.74 Itaconate*MUDMA + HEA- 5.14 0.17 152.87 57.14 3.52 2.12 ItaconateMUDMA + PCL- 2.70 0.26 126.67 8.02 9.04 5.33 Itaconate (2:1)MUDMA + PCL- 2.07 0.14 106.34 7.63 8.25 3.23 Itaconate (1:1)MUDA + PCL- 1.72 0.10 75.85 8.30 6.70 3.92Itaconate*ambient cure.UDMA - urethane dimethacrylate; MUDMA - methylurethane dimethacrylate; MUD A -methylurethane diacrylate.OONadic-HEACU2025-112-PCT (RGC0035PCT)PCL-ltaconateooDDSA-HEAHEA-ltaconateExample 2.

[0062] Table 3 presents properties for cured compositions for thermal cure unless otherwise indicated.Polymer Flexural modulus, GPa Flexural strength, MPaa*UDMA / MAA 4.1 (0.3) 184.7 (23.2)a* MUDMA / MAA 3.7 (0.2)b181.3 (16.5)aDUDMA 2-Oo / MAA 6.1 (0.3)C224.2 (24.6)bDUDMA 3-Oi / MAA 5.1 (0.2)d224.3 (19.9)ba,bDUDMA 4-Oi / MAA 3.9 (0.2) 179.1 (22.9)aDUDMA 5-Oi / MAA 3.7 (0.2)b195.0 (14.6)a*Superscript letters within columns designate statistically significant differences (ANOVA, p<0.05. Tukey post-hoc test)

[0063] Monomers are UDMA (urethane dimethacrylate), MUDMA (monourethane dimethacrylate, and DUDMA (diurethane dimethacrylate). The number (or j) in the following structures refers to the carbon spacing between urethane groups, and “Oo” or “Oi” refer to paired urethane configurations as either oxygen-out or oxy gen-in, respectively. MAA = methacrylic acid.CU2025-112-PCT (RGC0035PCT)UDMAMUDMADUDMA-2(Oo)DUDMA-j(Oi)

[0064] The data in Table 3 demonstrate that modulus and strength values of clustered urethanes (2-3 carbon spacer between urethanes), when copolymerized with MAA, are significantly greater than comparable urethane-acid copolymers involving greater spacing between the urethane groups or with single urethane functionality.

[0065] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

[0066] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0067] The terms “a” and “an” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. The term “or” means “and / or”. ReferenceCU2025-112-PCT (RGC0035PCT)throughout the specification to “one aspect”, “another aspect”, “an aspect”, and so forth, means that a particular element (e.g., feature, structure, and / or characteristic) described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity).

[0068] The endpoints of all ranges directed to the same component or property are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges (e.g., ranges of “up to about 25 wt.%, or, more specifically, about 5 wt.% to about 20 wt.%.” is inclusive of the endpoints and all intermediate values of the ranges of “about 5 wt.% to about 25 wt.%,” such as about 10 wt% to about 23 wt%, etc.).

Claims

CU2025-112-PCT (RGC0035PCT)CLAIMS1. A urethane (meth)acrylate monomer, comprising2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms;wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; andwherein the urethane (meth) acrylate monomer comprises at least one of the followingwherein each occurrence of X independently is hydrogen or methyl; and each occurrence of R1is independently hydrogen or, together with the O, an ether, ester, carbonate, or urethane (carbamate) group.

2. The urethane (meth)acrylate monomer of claim 1, wherein the urethane (meth)acrylate monomer comprises 2, 3, 4, 5, or 6 urethane groups and comprises 2, 3, 4, 5, or 6 (meth)acrylate groups.

3. The urethane (meth)acrylate monomer of claim 1, wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 4,000 grams / mole, or 3,000 grams / mole, or 2,000 grams / mole, or 1,000 grams / mole or 500 grams / mole, or 150 grams / mole.CU2025-112-PCT (RGC0035PCT)4. The urethane (meth)acrylate monomer of claim 1, wherein R1is hydrogen.

5. The urethane (meth)acrylate monomer of claim 1, wherein R1is methyl.

6. The urethane (meth) acrylate monomer of claim 1, prepared from (2-oxo-l,3-dioxolan-4-yl)methyl methacrylate. CAS# 13818-44-5 or (2-oxo-l,3-dioxolan-4-yl)methyl prop-2-enoate, CAS# 7528-90-7.

7. The urethane (meth)acrylate monomer of claim 1, wherein the urethane (meth)acrylate monomer isCU2025-112-PCT (RGC0035PCT)CU2025-112-PCT (RGC0035PCT)wherein each occurrence of X independently is hydrogen or methyl; each occurrence of R2is alkyl, alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or alkylarylalkyl; each occurrence of R3independently is alkyl, aryl, or alkylaryl; each occurrence of R4independently is alkyl, aryl, or alkylaryl; and each occurrence of R8independently is alkyl,CU2025-112-PCT (RGC0035PCT)A H^N-lChWg-* * — (H2C)1>sN *-(H2C)l V Y (CH2)I-8“* N— (CH2)1.8_*O O, orN-^O^-N * — (H2C)1.8— N N— (CH2)I-8-*o o8. A curable composition, comprising the urethane (meth)acrylate monomer of any one of claims 1 to 7; andan acidic or latent acidic comonomer, wherein the acidic or latent acidic comonomer is methacrylic acid, acrylic acid, itaconic acid, mono-2-(methacryloyloxy)ethyl maleate, 2-carboxy ethyl acrylate, 2-carboxy ethyl methacrylate, mono-2- (methacryloyloxy)ethyl succinate, (meth)acrylic anhydride, itaconic anhydride, maleic anhydride, 4-methacryloxyethyl methacrylate, 1,3-glycerol dimethacrylate / succinate adduct (CAS Reg. No. 107665-59-8), 1,3-glycerol dimethacrylate / maleate adduct, pyromellitic dianhydride, 4-methacryloxyethyl trimellitic acid, mono-2- (methacryloyloxy )ethyl succinate (MMES), mono-2-(methacryloyloxy)ethyl maleate (MMEM), mono-2-(acryloyloxy)ethyl itaconate (MAEI), acrylated nadic or carbic anhydride obtained from ring-opened cyclic anhydride with 2-hydroxyethyl (meth)acrylate, a ring-opened cyclic anhydride with a hydroxy functionalized (meth)acrylate, or a combination thereof.

9. The curable composition of claim 7, comprising the urethane (meth)acrylate monomer and the acidic or latent acidic comonomer in amounts such that a molar ratio of urethane groups in the urethane (meth)acrylate monomer to carboxylic acid and carboxylic acid anhydride groups in the acidic or latent acidic comonomer is 1:5 to 5:

1. or 1:4 to 4:1, or 1:3 to 3:1, or 1:3 to 1:1, or 1:1.5 to 1:2.5.

10. The cured composition of any one of claims 8 to 9.CU2025-112-PCT (RGC0035PCT)11. An article comprising the cured composition of claim 10.

12. A curable composition comprising,an acidic or latent acidic comonomer that is mono-2-(methacryloyloxy)ethyl succinate (MMES), mono-2-(methacryloyloxy)ethyl maleate (MMEM), mono-2- (aery loyloxy)ethyl itaconate (MAEI), acrylated nadic or carbic anhydride obtained from ring-opened cyclic anhydride with 2-hydroxyethyl (meth)acrylate, a ring-opened cyclic anhydride with a hydroxy functionalized (meth)acrylate, or a combination thereof; anda urethane (meth) acrylate monomer comprising 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane (meth) acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole;wherein a molar ratio of urethane groups in the urethane (meth)acrylate monomer to carboxylic acid and carboxylic acid anhydride groups in the acidic or latent acidic comonomer is 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1.

13. The curable composition of claim 12, wherein the acidic or latent acidic comonomer isCU2025-112-PCT (RGC0035PCT)CU2025-112-PCT (RGC0035PCT)a reaction product of a hydroxyl functionalized (meth)acrylate compound (left) and an anhydride compound (right):CU2025-112-PCT (RGC0035PCT)wherein each occurrence of X independently is hydrogen or methyl; each occurrence of y independently is 0 to 10; each occurrence of p independently is 1 to 10; each occurrence of q independently is 1 to 10; each occurrence of R9independently is alkyl; each occurrence of R10independently is alkyl.

14. The cured composition of any one of claims 12 to 13.

15. An article comprising the cured composition of claim 14.

16. A curable composition comprisinga monovinyl multiurethane monomer comprising a single vinyl group and 2 to 12 urethane groups wherein each of at least two urethane groups is separated from at least one other urethane group by at most three carbon atoms;CU2025-112-PCT (RGC0035PCT)a urethane (meth)acrylate monomer; andoptionally further comprising an acidic monomer.

17. The curable composition of claim 16, wherein the monovinyl multiurethane monomer iswherein each occurrence of X independently is hydrogen or methyl; each occurrence of R3independently is alkyl, aryl, or alkylaryl; and each occurrence of R4independently is alkyl, aryl, or alkylaryl.

18. The curable composition of claim 16 or 17, wherein the monovinyl multiurethane monomer has a molecular weight of less than or equal to 2000 grams / mole.

19. The curable composition of any one of claims 16 to 18, wherein the urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane(meth) acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole.

20. The curable composition of any one of claims 16 to 18, wherein the urethane (meth) acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; wherein the urethane (meth)acrylateCU2025-112-PCT (RGC0035PCT)monomer has a molecular weight less than or equal to 5,000 grams / mole; and wherein the urethane (meth)acrylate monomer comprises at least one of the following groups:O OOwherein each occurrence of X independently is hydrogen or methyl; and each occurrence of R1is independently hydrogen or together with the O an ether, ester, carbonate, or urethane (carbamate) group.

21. The cured composition of any one of claims 16 to 20.

22. An article comprising the cured composition of claim 21.

23. A monourethane multivinyl monomer, comprising one urethane group and 2 to 6 (meth)acrylate groups;wherein the monourethane multivinyl monomer has a molecular weight of greater than or equal to 150 grams / mole to less than or equal to 1,500 grams / mole.

24. The monourethane multi vinyl monomer of claim 23, that iswherein each occurrence of X independently is hydrogen or methyl; and f is 0 to 10;CU2025-112-PCT (RGC0035PCT)GMEC-EA 3-Amino-1,2-propanediol - EC25. A curable composition comprising the monourethane multivinyl monomer of claim 23 or 24, optionally further comprising a urethane (meth)acrylate monomer, an acidic monomer, or both a urethane (meth)acrylate monomer and an acidic monomer.

26. The curable composition of claim 25, wherein the urethane (meth)acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; and wherein the urethane (meth)acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; orwherein the urethane (meth) acrylate monomer comprises 2 to 12 urethane groups and 2 to 12 (meth)acrylate groups, wherein each of at least two urethane groups is separated from at least one other urethane group or at least one urea group by at most three carbon atoms; wherein the urethane (meth) acrylate monomer has a molecular weight less than or equal to 5,000 grams / mole; and wherein the urethane (meth)acrylate monomer comprises at least one of the following groups:CU2025-112-PCT (RGC0035PCT)wherein each occurrence of X independently is hydrogen or methyl; and each occurrence of R1is independently hydrogen or together with the O an ether, ester, carbonate, or urethane (carbamate) group.

27. The cured composition of any one of claims 23 to 26.

28. An article comprising the cured composition of claim 27.

29. An oligomeric clustered urethane comprises:a) the reaction product of monourethane diol produced from the ring-opening of ethylene carbonate with ethanolamine in reaction with a diisocyanate to give oligomeric clustered urethane; orb) a diurethane diol from ethylene carbonate (EC) plus ethylenediamine can be used to construct clustered tetraurethane segments.

30. The oligomeric clustered urethane of claim 29, whereina) isCU2025-112-PCT (RGC0035PCT)wherein each occurrence of X independently is hydrogen or methyl; each occurrence of R6independently is alkyl, alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or alkylarylalkyl; and g is 1 to 500; andb) iswherein each occurrence of R2independently is alkyl, alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or alkylarylalkyl; each occurrence of R6independently is alkyl, alkyl with 1 or more internal heteroatoms, alkyl with 1 or more pendent groups, aryl, or alkylarylalkyl; n is 1 to 500; and m is 1 to 500.

31. A curable composition comprising the oligomeric clustered urethane of claim 29 or 30, optionally further comprising one or more of a urethane monomer, an acidic monomer, a monovinyl multiurethane monomer, and a monourethane multivinyl monomer.

32. An article comprising the cured composition of claim 31.

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