Ophthalmic lens materials and devices made therefrom

Abstract

Disclosed are compositions made from reactive monomer mixtures and possessing both a high refractive index and a high Abbe number. These materials are highly suitable for use as implantable ophthalmic devices, with refractive indices that can be edited by the application of energy. When used in intraocular lenses, the high refractive index allows for thin lenses that compress easily through small incisions. Some compositions are suitable for use as intraocular lenses, phakic intraocular lenses, contact lenses, orthokeratology lenses, rigid gas-permeable lenses, corneal inlays, corneal outlays, or corneal inserts.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Application No. 63 / 429,512 (filed December 1, 2022), the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention relates to compositions made from reactive monomer mixtures that, upon polymerization, form polymer networks with high refractive indices and high Abbe numbers. These materials, which may have editable refractive indices, are designed for use in ophthalmic devices such as intraocular implants, intraocular lenses, phakic intraocular lenses, contact lenses, orthokeratology lenses, rigid gas permeable lenses, corneal inlays, corneal outlays, or corneal inserts. [Background technology]

[0003] Cataract surgery is typically performed to replace the natural lens of the eye, which has become opaque. Materials used to replace the natural lens must be soft and highly flexible so that, when formed into a lens, they can fold and pass through an incision, typically about 2 millimeters in size. Furthermore, materials must have excellent transparency and little or no sheen. Having a high refractive index allows for the use of thinner lenses. Materials with a high Abbe number exhibit less dispersion, which in turn allows for improved optical results and less light scattering. The combination of a high refractive index with a high Abbe number provides optical properties suitable for ophthalmic materials.

[0004] One of the first patents in this field, U.S. Patent No. 4,573,998 to Mazzocco, discloses a deformable intraocular lens that can be rolled to fit through a relatively small incision. The deformable lens is inserted into the eye while held in a rolled configuration and then released within the chamber. The lens' elastic properties allow it to return to its molded shape after insertion into the eye. Mazzocco discloses polyurethane elastomers, silicone elastomers, hydrogel polymer compounds, organic or synthetic gel compounds, and combinations thereof as suitable materials for the deformable lens.

[0005] Intraocular lenses can be damaged during implantation, for example, by frictional forces from the delivery device. To overcome this problem, some delivery devices are coated to provide extra lubricity. For example, U.S. Patent No. 8,323,799 to Hu discloses a soft, flexible, highly lubricious coating for polymeric insertion cartridges that allows for easy insertion of intraocular lenses through small-bore cartridges suitable for use in small (less than 3 mm) incisions. While such coatings are useful, there is a need for materials that exhibit a balance of physical and mechanical properties to allow insertion through small-diameter incisions as well as to restore their original shape and function after placement in the eye. Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, there is a need for materials with relatively high refractive indices and Abbe numbers that can be formed into flexible intraocular lenses that can be folded into a compact configuration for insertion through a small incision and then expanded to their original form at the implantation site. [Means for solving the problem]

[0007] The present invention relates to a composition suitable for use in an ophthalmic device, such as an intraocular lens, a phakic intraocular lens, an intraocular implant, an orthokeratology lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert, which is prepared by free radical polymerization of a reactive monomer mixture comprising: a) a compatibilizing monomer selected from the group consisting of pendant carbamate monomers, pendant amide monomers, and combinations thereof; b) a cross-linking agent; c) ethylene glycol dicyclopentenyl ether (meth)acrylate, The concentration of ethylene glycol dicyclopentenyl ether (meth)acrylate in the reactive monomer mixture, excluding any diluent, is 20 weight percent or greater, and the composition exhibits a refractive index of at least 1.45 and an Abbe number of at least 39.

[0008] In one aspect, the pendant carbamate monomer is represented by formula I, P g -L-OCONR 1 R 2 In another aspect, the pendant amide monomer has a chemical structure described by Formula II, P g -L-CONR 1 R 2 In Formula I and Formula II, P g is a polymerizable group, L is a linking group, and R 1 and R 2 is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, and heteroaryl groups.

[0009] In some particular aspects of the present invention, the compatibilizing monomer has the chemical structure shown in Formula III and Formula IV:

[0010] [ka] In the formula, R 1 and R 2 is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; R 3 is H or methyl.

[0011] The present invention also relates to novel compounds having the chemical structure shown in Formula IV, suitable for the production of ophthalmic devices by free radical polymerization. For example, homopolymers, copolymers, and crosslinked networks derived from monomers of Formula IV can be used to produce various ophthalmic devices, such as intraocular lenses, phakic intraocular lenses, intraocular implants, contact lenses, corneal inlays, corneal outlays, or corneal inserts, as well as formulation components such as plasticizers in intraocular lenses, wetting agents in contact lenses or eye drops, and additives to packaging solutions for contact lenses. The copolymers can be block or graft copolymers, including, but not limited to, diblock and triblock copolymers and segmented block copolymers. The crosslinked networks can be water-swellable or non-water-swellable. Depending on their composition, the crosslinked networks can be hydrogels or silicone hydrogels if the equilibrium water content is sufficiently high. The crosslinked networks can also be used to produce orthokeratology lenses and rigid gas-permeable lenses. The present invention further relates to a method for synthesizing a compound of formula IV, comprising the steps of: (a) reacting an amine with methyl glycolate to form an N-alkyl-2-hydroxyacetamide; and (b) reacting the N-alkyl-2-hydroxyacetamide with (meth)acryloyl chloride.

[0012] In another aspect, the present invention provides a method for manufacturing an ophthalmic device, the method comprising: (a) providing a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate; and (b) forming an ophthalmic device; alternatively, (a) molding a device from a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate; alternatively, (a) providing a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate in a mold assembly; (b) forming an ophthalmic device; and (c) removing the ophthalmic device from the mold assembly; alternatively, (a) providing a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate in a mold assembly; (b) forming the ophthalmic device by a photopolymerization reaction; and (c) removing the ophthalmic device from the mold assembly.

[0013] In certain aspects of any of the above-described methods of manufacturing an ophthalmic device, the method further comprises extracting the ophthalmic device with a solvent, further comprises hydrating the extracted ophthalmic device with at least one aqueous solution, further comprises sterilizing the ophthalmic device, and further comprises irradiating using a laser either before or after sterilization, including after the ophthalmic device is implanted in a human. [Brief explanation of the drawings]

[0014] [Figure 1] 1 shows UV-VIS transmission spectra of HEVB and HEVC in 0.2 mM methanol. [Figure 2] 1 shows the UV-VIS transmission spectra of the disks of Examples 8, 10 and 11. [Figure 3] 1 shows the UV-VIS transmission spectra of the disks of Examples 12 and 13. [Figure 4] 1 shows UV-VIS transmission spectra of the disks of Examples 126 to 130. DETAILED DESCRIPTION OF THE INVENTION

[0015] A.Definition It is to be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description, as the present disclosure is capable of other embodiments and of being practiced or being carried out in various ways using the teachings set forth herein.

[0016] The following definitions are provided for terms used in this disclosure. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The definition of polymer is consistent with the definition disclosed in Compendium of Polymer Terminology and Nomenclature, IUPAC Recommendations 2008, edited by: Richard G. Jones, Jaroslav Kahovec, Robert Stepto, Edward S. Wilks, Michael Hess, Tatsuki Kitayama, and W. Val Metanomski. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0017] "Target polymer" means a polymer that has been synthesized from a reactive monomer mixture, including monomers, macromers, prepolymers, crosslinkers, initiators, additives, diluents, and the like.

[0018] A "polymer" is an organic compound with a number-average molecular weight greater than 1500 Daltons, and may be reactive or non-reactive. The number-average molecular weight, weight-average molecular weight, and polydispersity of a polymer sample are typically measured by gel permeation or size-exclusion chromatography using refractive index, UV, and / or light scattering detectors. Reference standards can be used to calibrate the chromatograph.

[0019] The term "polymerizable compound" means a compound that contains one or more polymerizable groups. This term includes, for example, monomers, macromers, oligomers, prepolymers, crosslinkers, and the like.

[0020] A "polymerizable group" is a group capable of undergoing free radical and / or ionic polymerization (e.g., cationic polymerization), e.g., chain growth polymerization, such as a carbon-carbon double bond that can polymerize when subjected to radical polymerization initiation conditions. Non-limiting examples of free radical polymerizable groups include (meth)acrylate, styrene, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, and other vinyl groups. Preferably, the free radical polymerizable group comprises (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, and styryl functional groups, as well as mixtures of any of the foregoing. More preferably, the free radical polymerizable group comprises (meth)acrylate, (meth)acrylamide, and mixtures thereof. The polymerizable group may be unsubstituted or substituted. For example, the nitrogen atom in (meth)acrylamide may be bonded to hydrogen, or the hydrogen may be replaced by alkyl or cycloalkyl (which may themselves be further substituted).

[0021] Any type of free radical polymerization can be used, including but not limited to bulk, solution, suspension, and emulsion, as well as any controlled radical polymerization method, such as stable free radical polymerization, nitroxide-mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium-mediated living radical polymerization, etc.

[0022] A "monomer" is a monofunctional molecule capable of undergoing chain-growth polymerization, particularly free-radical polymerization, thereby creating repeat units within the chemical structure of a target polymer. A "repeating unit" is the smallest group of atoms within a polymer that corresponds to the polymerization of a particular monomer or macromer. Some monomers have difunctional impurities that can act as crosslinkers. A "hydrophilic monomer" is a monomer that produces a clear, single-phase solution when mixed with deionized water at 25°C at a concentration of 5 weight percent, such as N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA), N-vinylmethacetamide (VMA), and N-vinyl-N-methylacetamide (NVA). A "hydrophilic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that produces a clear, single-phase solution when mixed with deionized water at 25°C at a concentration of 5 weight percent. A "hydrophobic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that is slightly soluble or insoluble in deionized water at 25°C.

[0023] A "macromonomer" or "macromer" is a polymer having one group capable of undergoing chain-growth polymerization, particularly free-radical polymerization, thereby creating repeat units within the chemical structure of a target polymer. Generally, the chemical structure of a macromer differs from that of the target polymer; i.e., the repeat units of the pendant group of the macromer differ from the repeat units of the target polymer or its backbone. The only differences between a monomer and a macromer are the chemical structure of the pendant group, the molecular weight, and the molecular weight distribution. Consequently, and as used herein, patent literature sometimes defines a monomer as a polymerizable compound having a relatively low molecular weight of about 1,500 daltons or less, which essentially includes some macromers. Specifically, monomethacryloxypropyl-terminated, mono-n-butyl-terminated polydimethylsiloxane (number average molecular weight = 500-1500 g / mol) (mPDMS) and mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated, mono-n-butyl-terminated polydimethylsiloxane (number average molecular weight = 500-1500 g / mol) (OH-mPDMS) may be referred to as monomers or macromers. Furthermore, patent literature sometimes defines macromers as having one or more polymerizable groups, essentially expanding the general definition of macromer to include prepolymers. Consequently, and as used herein, difunctional and multifunctional macromers, prepolymers, and crosslinkers may be used interchangeably.

[0024] A "polymer" is a target macromolecule composed of repeating units of the monomers used during polymerization. A "homopolymer" is a polymer made from one monomer, a "copolymer" is a polymer made from two or more monomers, and a "terpolymer" is a polymer made from three monomers. A "block copolymer" consists of compositionally distinct blocks or segments. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A "comb or graft copolymer" is made from at least one macromer.

[0025] An "initiator" or "free radical polymerization initiator" is a molecule that can decompose into radicals that can subsequently react with monomers to initiate a free radical polymerization reaction. Thermal initiators decompose at a specific rate depending on the temperature; typical examples include azo compounds such as 1,1'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid); peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroyl peroxide; peracids such as peracetic acid and potassium persulfate; and various redox systems. Photoinitiators decompose via a photochemical process; typical examples include derivatives of benzil, benzoin, acetophenone, benzophenone, camphorquinone, and mixtures thereof, as well as various monoacyl and bisacylphosphine oxides and combinations thereof.

[0026] A "crosslinker" is a di- or polyfunctional monomer or macromer that can undergo free radical polymerization at two or more positions on the molecule, thereby creating branch points and polymer networks. Common examples are ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylene bisacrylamide, triallyl cyanurate, etc.

[0027] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can undergo further reaction to form a polymer.

[0028] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0029] As used herein, the term "(meth)" refers to optional methyl substitution. Thus, a term such as "(meth)acrylate" refers to both methacrylate and acrylate.

[0030] Wherever a chemical structure is depicted, it should be understood that the disclosed alternatives for substituents in the structure may be combined in any combination. Thus, when a structure contains a substituent R * and R ** and each of these contains a list of three possible groups, then nine combinations are disclosed. The same is true for combinations of properties.

[0031] General formula [ *** ] n When a subscript, such as "n" in * is used to denote the number of repeat units in a chemical formula of a polymer, the formula should be interpreted as representing the number average molecular weight of the polymer.

[0032] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0033] Unless otherwise stated, a numerical range such as, for example, "2 to 10" is inclusive of the numbers defining the range (eg, 2 and 10).

[0034] The terms "reactive mixture" and "reactive monomer mixture" refer to a mixture of components (retained and unretained) that, when mixed together and subjected to polymerization conditions, result in the formation of a polymer network and biomedical devices, ophthalmic devices, intraocular implants, contact lenses, and intraocular lenses made therefrom. The reactive mixture may include retained components such as monomers, macromers, prepolymers, crosslinkers, and initiators; additives such as wetting agents, polymers, dyes, UV / HEV absorbers, pigments, light-absorbing compounds such as photochromic compounds, pharmaceutical compounds, and / or nutraceutical compounds, which may be reactive or non-reactive but can be retained in the resulting biomedical device. The reactive mixture may also contain unretained components, such as diluents, that are intended to be removed from the device prior to use. It will be understood that a variety of additives may be added depending on the biomedical device being made and its intended use. The concentrations of the components of the reactive mixture are expressed as a weight percent of all retained components in the reactive mixture, thus excluding unretained components such as diluents. When diluents are used, their concentrations are expressed as weight percent based on the amounts of all components (including the diluent) in the reactive mixture.

[0035] "Reactive components" are components in the reactive monomer mixture that become part of the structure of the polymer network of the resulting composition. Diluents and processing aids that do not become part of the structure of the polymer are not reactive components.

[0036] "Retained components" are polymerizable compounds (such as monomers, macromers, oligomers, prepolymers, and crosslinkers) in the reactive mixture, as well as any other components intended to substantially remain in the polymeric network after polymerization and after all post-processing steps (such as extraction steps) and packaging steps are complete. Retained components may be retained within the polymer network by covalent bonds, hydrogen bonds, electrostatic interactions, formation of an interpenetrating polymer network, or any other means. Components intended to be released from the biomedical device during use are still considered "retained components." For example, pharmaceutical or nutraceutical components in contact lenses intended to be released during wear are considered "retained components." Components, such as diluents, that are intended to be removed from the polymer network during the manufacturing process (e.g., by extraction) are "non-retained components."

[0037] "Alkyl" and "aliphatic" are used interchangeably herein and refer to an optionally substituted straight- or branched-chain alkyl group containing the specified number of carbon atoms. When no number is specified, the alkyl (including any optional substituents thereon) can contain any of 1 to 24 carbon atoms, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24 carbon atoms. Preferably, the alkyl group contains 1 to 18 carbon atoms, including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and 18 carbon atoms. Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, iso-, sec-, and tert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like. Examples of substituents on alkyl include one, two, or three groups independently selected from hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. "Alkylene" refers to a divalent alkyl group, such as -CH-, -CHCH-, -CHCHCH-, -CHCH(CH)CH-, and -CHCHCHCHCH-.

[0038] "Amide" or "amide" refers to a moiety having the formula -C(=O)NRR' or -NRC(=O)R', where R and R' are each independently selected from the group consisting of hydrogen and alkyl. When the amide moiety is -C(=O)NRR', R and R' may optionally be joined together with the nitrogen to which they are attached to form a 4-, 5-, 6-, or 7-membered ring.

[0039] "Amidoalkyl" refers to an alkyl group, as defined above, that is substituted with one or more amido groups. Preferred amidoalkyl groups contain 1 to 6 carbons, 1 to 4 carbons, or 1 to 2 carbons.

[0040] The term "halogen" or "halo" refers to fluorine, chlorine, bromine, and iodine. A preferred halogen is F.

[0041] "Haloalkyl" refers to an alkyl group, as defined above, substituted by one or more halogen atoms, where each halogen is independently F, Cl, Br, or I. A preferred halogen is F. Preferred haloalkyl groups contain 1 to 6 carbons, 1 to 4 carbons, or 1 to 2 carbons. "Haloalkyl" includes perhaloalkyl groups, e.g., -CF3 or -CF2CF3, in which each hydrogen atom of the alkyl group is replaced with a halogen atom. "Haloalkylene" refers to divalent haloalkyl groups such as -CH2CF2- and -CF2CF2-.

[0042] "Hydroxy" refers to the group --OH.

[0043] "Hydroxyalkyl" refers to an alkyl group, as defined herein, substituted with at least one hydroxy group. Representative examples of hydroxyalkyl include, but are not limited to, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 2,3-dihydroxypentyl, 4-hydroxybutyl, 2-ethyl-4-hydroxyheptyl, 3,4-dihydroxybutyl, and 5-hydroxypentyl.

[0044] "Cycloalkyl" and "alicyclic" are used interchangeably herein and refer to an optionally substituted cyclic hydrocarbon containing a specified number of ring carbon atoms. If no number is specified, the cycloalkyl may contain 3 to 20 ring carbon atoms (e.g., 3 to 12 ring carbon atoms). Alicyclic groups can be monocyclic, bicyclic, tricyclic, bridged, fused, and / or spirocyclic. Alicyclic groups can also have one or more double bonds, provided the group is not fully aromatic. Preferred monocyclic alicyclic groups are C3-C8 cycloalkyl groups, C3-C7 cycloalkyl, more preferably C4-C7 cycloalkyl, and even more preferably C5-C6 cycloalkyl. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on cycloalkyl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, thioalkyl, amido, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Cycloalkylene" refers to a divalent cycloalkyl group such as 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene. "Cycloalkyl(alkyl)" group refers to an alkyl group as defined above having at least one cycloalkyl substituent, for example, cyclohexylmethyl, cyclohexylethyl, and cyclohexylpropyl.

[0045] "Heterocycloalkyl" refers to a cycloalkyl ring or ring system, as defined above, in which at least one ring carbon is replaced by a heteroatom selected from nitrogen, oxygen, and sulfur. The heterocycloalkyl ring is optionally fused or otherwise attached to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings and / or phenyl rings. Preferred heterocycloalkyl groups have 5 to 7 members. More preferred heterocycloalkyl groups have 5 or 6 members. "Heterocycloalkylene" refers to a divalent heterocycloalkyl group.

[0046] "Aryl" refers to an optionally substituted aromatic hydrocarbon ring system containing at least one aromatic ring. The aryl group contains the designated number of ring carbon atoms. If no number is designated, the aryl may contain 6 to 14 ring carbon atoms. The aromatic ring may optionally be fused or otherwise attached to other aromatic or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Preferred examples of aryl groups include phenyl. Examples of substituents on aryl groups include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Arylene" refers to a divalent aryl group, such as 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

[0047] "Arylalkyl" refers to an aryl group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein. Representative examples of arylalkyl include phenylmethyl (i.e., benzyl), phenylethyl, and phenylpropyl.

[0048] "Heteroaryl" refers to an aryl ring or ring system, as defined above, in which at least one ring carbon atom is replaced by a heteroatom selected from nitrogen, oxygen, and sulfur. The heteroaryl ring may be fused to or otherwise bonded to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocycloalkyl rings. Examples of heteroaryl groups include pyridyl, furyl, and thienyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0049] "Heteroarylalkyl" refers to a heteroaryl group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein. Representative examples of arylalkyl include thiophen-2-ylmethyl, furan-2-ylmethyl, and pyridylmethyl.

[0050] "Alkoxy" refers to an alkyl group attached to the parent molecular moiety through an oxygen bridge. Examples of alkoxy groups include, for example, methoxy, ethoxy, propoxy, and isopropoxy. "Thioalkyl" refers to an alkyl group attached to the parent molecular moiety through a sulfur bridge. Examples of thioalkyl groups include, for example, methylthio, ethylthio, n-propylthio, and isopropylthio. "Aryloxy" refers to an aryl group attached to the parent molecular moiety through an oxygen bridge. An example includes phenoxy. "Arylthio" refers to an aryl group attached to the parent molecular moiety through a sulfur bridge. An example includes phenylthio. "Cyclicalkoxy" refers to a cycloalkyl group attached to the parent moiety through an oxygen bridge.

[0051] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with at least one alkoxy group. Representative examples of alkoxyalkyl include, but are not limited to, methoxymethyl, 2-methoxyethyl, and 3-methoxypropyl.

[0052] "Alkylamine" refers to an alkyl group attached to the parent molecular moiety through an -NH bridge. Alkyleneamine refers to a divalent alkylamine group, such as -CHCHNH-.

[0053] "Alkyleneoxy" refers to a group having the general formula -(alkylene-O-) p -or -(O-alkylene) p" refers to the group -, where alkylene is as defined above, p is 1 to 200, or 1 to 100, or 1 to 50, or 1 to 25, or 1 to 20, or 1 to 10, and each alkylene is independently optionally substituted with one or more groups independently selected from hydroxyl, halo (e.g., fluoro), amino, amido, ether, carbonyl, carboxyl, and combinations thereof. When p is greater than 1, each alkylene may be the same or different, and the alkyleneoxy may be in a block or random configuration. When the alkyleneoxy forms a terminal group in a molecule, the terminus of the alkyleneoxy may be, for example, hydroxy or alkoxy (e.g., HO-[CHCHO] p - or CHO-[CHCHO] p Examples of alkyleneoxy include polyethyleneoxy, polypropyleneoxy, polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

[0054] "Oxaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced by an oxygen atom, such as -CHCHOCH(CH)CH-. "Thiaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced by a sulfur atom, such as -CHCHSCH(CH)CH-.

[0055] The term "linking group" refers to a moiety that connects a polymerizable group to a parent molecule. The linking group can be any moiety that is compatible with the compound of which it is a part, does not undesirably interfere with the polymerization of the compound, and is stable under the conditions of polymerization, as well as under the conditions of processing and storage of the final product. For example, the linking group can be a bond or can include one or more alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, ester (-CO-), arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted with one or more halo groups, e.g., -OCF-, -OCFCF-, -OCFCH-), siloxanyl, alkylenesiloxanyl, or combinations thereof. The linking group may be optionally substituted with one or more substituents. Suitable substituents can include those independently selected from alkyl, halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, MeO-alkyleneoxy, siloxanyl, siloxy, siloxy-alkyleneoxy-, siloxy-alkylene-alkyleneoxy- (two or more alkyleneoxy groups can be present, and each methylene in the alkylene and alkyleneoxy is independently optionally substituted with hydroxyl), ether, amine, carbonyl, carbamate, and combinations thereof. The linking group can also be substituted with a polymerizable group (in addition to the polymerizable group to which it is connected), such as (meth)acrylate.

[0056] Preferred linking groups include C1-C8 alkylene (preferably C2-C6 alkylene) and C1-C8 oxaalkylene (preferably C2-C6 oxaalkylene), each of which is optionally substituted with one or two groups independently selected from hydroxyl and siloxy. Preferred linking groups also include ester, amide, C1-C8 alkylene-ester-C1-C8 alkylene, or C1-C8 alkylene-amide-C1-C8 alkylene.

[0057] The term "electron withdrawing group" (EWG) refers to a chemical group that withdraws electron density from the atom or group of atoms to which it is bonded. Examples of EWGs include, but are not limited to, cyano, amide, ester, keto, or aldehyde.

[0058] When the compounds described herein contain olefinic double bonds or other centers of geometric asymmetry, and unless otherwise specified, the compounds are intended to include the cis, trans, Z-, and E-configurations, as well as all tautomeric and salt forms.

[0059] The term "light absorbing compound" refers to a chemical substance that absorbs light within the visible spectrum (e.g., in the range of 380 nanometers to 780 nanometers). A "high-energy radiation absorber," "UV / HEV absorber," "UV / HEV absorbing compound," or "high-energy light absorbing compound" is a chemical substance that absorbs various wavelengths of ultraviolet radiation, high-energy visible light, or both. The ability of a material to absorb light of a particular wavelength can be determined by measuring its UV / VIS transmittance spectrum. A compound that exhibits no absorption at a particular wavelength exhibits substantially 100 percent transmittance at that wavelength. Conversely, a compound that completely absorbs at a particular wavelength exhibits substantially 0% transmittance at that wavelength.

[0060] "Silyl" refers to a structure of formula R3Si-, and "siloxy" refers to a structure of formula R3Si-O-, where each R in silyl or siloxy is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl or ethyl), and C3-C8 cycloalkyl.

[0061] "Siloxanyl" refers to a structure having at least one Si-O-Si bond. Thus, for example, a siloxanyl group refers to a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxanyl compound refers to a compound having at least one Si-O-Si group. "Siloxanyl" refers to monomers (e.g., Si-O-Si) as well as oligomeric / polymeric structures (e.g., [Si-O] n where n is 2 or greater. Each silicon atom in the siloxanyl group is independently selected to complete their valence. A Group (R A is replaced by (as defined in options (b) to (i) of Formula A).

[0062] The "silicone-containing component" may include one or more polymerizable compounds of Formula A:

[0063] [ka] wherein at least one R A is the formula P g -L- group, where P g is a polymerizable group, L is a linking group, and the remaining R A are each independently a)P g -L- b) C1-C optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 16 Alkyl c) C3-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 12 cycloalkyl d) C6-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 14 Aryl e) Halo f) alkoxy, cyclic alkoxy, or aryloxy g) Siloxy h) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as, for example, polyethyleneoxyalkyl, polypropyleneoxyalkyl, or poly(ethyleneoxy-co-propyleneoxyalkyl), or i) a monovalent siloxane chain comprising 1 to 100 siloxane repeat units optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxy, alkylcarboxy, alkoxy, amido, carbamate, halo, or combinations thereof; In the formula, n is 0 to 500, or 0 to 200, or 0 to 100, or 0 to 20, and when n is other than 0, it is understood that n is a distribution having a mode equivalent to the indicated value. When n is 2 or more, the SiO units may be the same or different R A may carry substituents, different R A When substituents are present, the n groups may be in a random or block configuration.

[0064] In formula A, three R A may each contain a polymerizable group, alternatively two R A may each contain a polymerizable group, or alternatively one R A However, it may contain a polymerizable group.

[0065] When the linking group is comprised of a combination of moieties as described above (e.g., alkylene and cycloalkylene), the moieties may be present in any order. For example, in Formula A above, when L is shown to be -alkylene-cycloalkylene-, then P g -L, Pg -alkylene-cycloalkylene-, or P g -cycloalkylene-alkylene-. Regardless of this, the order of listing must be determined based on the order of the terminal polymerizable group (P g ) represents the preferred order in which the moieties appear in the compound. For example, in Formula A, if L is shown to be alkylene-cycloalkylene, then P g -L is preferably P g Some preferred silicone-containing components are mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane (mPDMS), mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminated polydimethylsiloxane (OH-mPDMS), 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate (SiMAA), and 3-(3-(1,5-di-tert-butyl-1,1,3,5,5-pentamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate (tBu-SiMAA).

[0066] The term "optional substituent" means that an underlying hydrogen atom is optionally replaced by a substituent. Any substituent that is sterically practical and synthetically feasible at the substitution site may be used. Identification of suitable optional substituents is within the ability of one of ordinary skill in the art. Examples of "optional substituents" include, but are not limited to, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR'R'', benzyl, SO3H, or SO3Na, where R' and R'' are independently H or C1-C6 alkyl. The foregoing substituents may be optionally substituted by optional substituents (which, unless otherwise indicated, are preferably not further substituted). For example, alkyl may be substituted by halo (e.g., resulting in CF3).

[0067] In some embodiments, the reactive monomer mixture includes at least one polyamide. As used herein, the term "polyamide" refers to polymers and copolymers containing repeating units containing amide groups. Polyamides may include cyclic amide groups, non-cyclic amide groups, and combinations thereof, and may be any polyamide known to those skilled in the art. Non-cyclic polyamides include pendant non-cyclic amide groups that are capable of association with hydroxyl groups. Cyclic polyamides include cyclic amide groups that are capable of association with hydroxyl groups. Suitable polyamides for use in the compositions and methods of the present disclosure are disclosed in U.S. Patent Application Publication No. 20180009922 to Alli et al., entitled SILICONE HYDROGELS COMPRISING HIGH LEVELS OF POLYAMIDES, published January 11, 2018, and U.S. Patent Application Publication No. 20180011222 to Alli et al., entitled SILICONE HYDROGELS COMPRISING POLYAMIDES, published January 11, 2018, each of which is incorporated herein by reference in its entirety. Some preferred polyamides are polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), and combinations thereof.

[0068] The term "individual" includes human and non-human vertebrates.

[0069] The term "biomedical device" refers to any article designed to be used in or on mammalian tissue or fluid, preferably human tissue or fluid. Examples of these devices include, but are not limited to, wound dressings, sealants, tissue prostheses, drug delivery systems, coatings, adhesion barriers, catheters, implants, stents, and ophthalmic devices such as intraocular implants, intraocular lenses, and contact lenses. The biomedical device may be an ophthalmic device, particularly an ophthalmic implant or ophthalmic lens made from the reactive monomer compositions described herein.

[0070] The term "ocular surface" includes the surface and glandular epithelium of the cornea, conjunctiva, lacrimal gland, accessory lacrimal gland, nasolacrimal duct, and meibomian gland, as well as their apical and basal matrices, puncta, and adjacent or associated structures, including the eyelids, which are connected as a functional system by both epithelial continuity through innervation and by the endocrine and immune systems.

[0071] The term "ophthalmic device" refers to any apparatus that resides in or on the eye or any part of the eye (including the ocular surface). These devices can provide optical correction, appearance enhancement, vision enhancement, therapeutic effects (e.g., as a bandage), or delivery of active ingredients such as pharmaceutical and nutritional supplements, or any combination of the foregoing. Examples of ophthalmic devices include, but are not limited to, lenses, optics, and ocular inserts (including, but not limited to, punctal plugs). "Lens" includes soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and overlay lenses. Ophthalmic devices may include intraocular implants, intraocular lenses, or contact lenses.

[0072] The term "contact lens" refers to an ophthalmic device that can be placed on the cornea of ​​an individual's eye. Contact lenses may provide corrective, cosmetic, or therapeutic benefits, including wound healing, delivery of medications or nutritional supplements, diagnostic evaluation or monitoring, ultraviolet (UV) light absorption, visible (VIS) light or glare reduction, or any combination thereof. Contact lenses may be of any suitable material known in the art and may be soft lenses, hard lenses, or hybrid lenses that include at least two distinct portions with different physical, mechanical, or optical properties, such as modulus of elasticity, water content, light transmission, or a combination thereof.

[0073] "Intraocular lens" refers to a lens implanted in the eye. In some embodiments, an intraocular lens is implanted in the eye to replace the existing lens (e.g., because the existing lens has become clouded by a cataract or as a form of refractive surgery to change the refractive power of the eye).

[0074] The "Abbe number", also known as the V number or astringency of a transparent material, is a measure of a material's dispersiveness, i.e., the change in refractive index with wavelength, with higher values ​​of V indicating lower dispersiveness. The Abbe number of a material is defined by the following formula: Abbe number V = (n D -1) / (n F -n C ), where n D , n F and n C are the refractive indices of the material at the wavelengths of the Fraunhofer D, F, and C spectral lines (589.3 nanometers, 486.1 nanometers, and 656.3 nanometers, respectively).

[0075] The "refractive index" of a medium is defined by the formula: refractive index n=c / v, where c is the speed of light in a vacuum and v is the phase velocity of light in the medium.

[0076] B. Composition In some aspects of the present invention, the presently disclosed subject matter provides compositions made by free radical polymerization of a reactive monomer mixture, the reactive monomer mixture comprising: (a) a pendant carbamate monomer having the chemical structure of Formula I, a pendant amide monomer having the chemical structure of Formula II, and combinations thereof; g -L-OCONR 1 R 2 and Formula II, P g -L-CONR 1 R 2 A compatibilizing monomer having the chemical structure: g is a polymerizable group, L is a linking group, and R 1 and R 2 is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, and heteroalkyl groups; and (b) a cross-linking agent; (c) ethylene glycol dicyclopentenyl ether (meth)acrylate, The concentration of ethylene glycol dicyclopentenyl ether (meth)acrylate in the reactive monomer mixture, excluding any diluent, is 20 weight percent or greater, and the composition exhibits a refractive index of at least 1.45 and an Abbe number of at least 39 ["Composition (A)"].

[0077] Non-limiting examples of the polymerizable group of the compatibilizing monomer in composition (A) include (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, styrene, vinyl ether, O-vinyl carbamate, O-vinyl carbonate, and other vinyl groups. Preferably, the polymerizable group comprises a (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide group, and mixtures thereof. More preferably, the polymerizable group comprises a (meth)acrylate, (meth)acrylamide, and combinations thereof. Most preferably, the polymerizable group comprises a (meth)acrylate.

[0078] Non-limiting examples of the linking group of the compatibilizing monomer in composition (A) include alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, ester, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, and haloalkyleneoxy. Preferred linking groups include ester, amide, C1-C8 alkylene, C1-C8 oxaalkylene, C1-C8 alkylene-ester-C1-C8 alkylene, and C1-C8 alkylene-amido-C1-C8 alkylene. More preferred linking groups include C1-C8 alkylene and C1-C8 oxaalkylene. Most preferred linking groups include C1-C8 alkylene. A particularly preferred linking group is unsubstituted C1-C4 alkylene.

[0079] In certain embodiments of the present invention, the compatibilizing monomer in composition (A) is a pendant carbamate monomer having the chemical structure shown in Formula III:

[0080] [ka] In the formula, R 1 and R 2is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; R 3 is H or methyl.

[0081] In another particular embodiment of the present invention, the compatibilizing monomer in composition (A) is a pendant amide monomer having the chemical structure shown in Formula IV:

[0082] [ka] In the formula, R 1 and R 2 is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; R 3 is H or methyl.

[0083] In yet another particular embodiment of the present invention, the compatibilizing monomer in composition (A) is a mixture of pendant carbamate monomers and pendant amide monomers.

[0084] R in Formulas III and IV 1 and R 2 Non-limiting examples of are independently hydrogen, C1-C 24 Straight chain alkyl groups, C1-C 24 Branched chain alkyl groups, C3-C 20 Cycloalkyl, cycloalkyl is C3-C 20 Cycloalkyl, alkyl is C1-C 24 Straight chain alkyl group or C1-C 24 cycloalkyl (alkyl) groups, branched chain alkyl groups, and combinations thereof, optionally substituted with hydroxy, alkoxy, or halogen. Preferably, R 1 and R2 are independently hydrogen, C1 to C 18 Straight chain alkyl groups, C1-C 18 More preferably, R is selected from the group consisting of alkyl, branched chain alkyl groups, and mixtures thereof, optionally substituted with hydroxy, alkoxy, or halogen. 1 and R 2 are independently hydrogen, unsubstituted C1-C 18 Straight chain alkyl groups, unsubstituted C1-C 18 Preferably, R is selected from the group consisting of alkyl groups, branched chain alkyl groups, and mixtures thereof. 1 and R 2 are independently selected from unsubstituted C1-C6 alkyl, or are independently selected from unsubstituted C1-C3 alkyl. More preferably, R 1 and R 2 are both methyl. Most preferably, R 1 is hydrogen and R 2 is unsubstituted C1~C 18 It is a straight chain alkyl group.

[0085] In one embodiment of the present invention, the compatibilizing monomer of composition (A) is 2-((methylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((ethylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((propylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((hexylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((octylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((nonylcarbamoyl)oxy)ethyl (meth)acrylate the pendant carbamate monomer is selected from the group consisting of 2-((decylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((undecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((dodecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tridecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tetradecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((hexadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptadecylcarbamoyl)oxy)ethyl (meth)acrylate, and combinations thereof.Preferably, the pendant carbamate monomer is 2-((methylcarbamoyl)oxy)ethyl acrylate, 2-((ethylcarbamoyl)oxy)ethyl acrylate, 2-((propylcarbamoyl)oxy)ethyl acrylate, 2-((butylcarbamoyl)oxy)ethyl acrylate, 2-((pentylcarbamoyl)oxy)ethyl acrylate, 2-((hexylcarbamoyl)oxy)ethyl acrylate, 2-((heptylcarbamoyl)oxy)ethyl acrylate, 2-((octylcarbamoyl)oxy)ethyl acrylate, 2-((nonylcarbamoyl)oxy) ethyl acrylate, 2-((decylcarbamoyl)oxy)ethyl acrylate, 2-((undecylcarbamoyl)oxy)ethyl acrylate, 2-((dodecylcarbamoyl)oxy)ethyl acrylate, 2-((tridecylcarbamoyl)oxy)ethyl acrylate, 2-((tetradecylcarbamoyl)oxy)ethyl acrylate, 2-((pentadecylcarbamoyl)oxy)ethyl acrylate, 2-((hexadecylcarbamoyl)oxy)ethyl acrylate, 2-((heptadecylcarbamoyl)oxy)ethyl acrylate, and combinations thereof. More preferably, the pendant carbamate monomer is selected from 2-((methylcarbamoyl)oxy)ethyl acrylate, 2-((ethylcarbamoyl)oxy)ethyl acrylate, 2-((propylcarbamoyl)oxy)ethyl acrylate, 2-((butylcarbamoyl)oxy)ethyl acrylate, 2-((pentylcarbamoyl)oxy)ethyl acrylate, 2-((hexylcarbamoyl)oxy)ethyl acrylate, 2-((heptylcarbamoyl)oxy)ethyl acrylate, 2-((octylcarbamoyl)oxy)ethyl acrylate, 2-((nonylcarbamoyl)oxy)ethyl acrylate, 2-((decylcarbamoyl)oxy)ethyl acrylate, and combinations thereof.Most preferably, the pendant carbamate monomer is selected from 2-((butylcarbamoyl)oxy)ethyl acrylate, 2-((pentylcarbamoyl)oxy)ethyl acrylate, 2-((hexylcarbamoyl)oxy)ethyl acrylate, 2-((heptylcarbamoyl)oxy)ethyl acrylate, 2-((octylcarbamoyl)oxy)ethyl acrylate, 2-((nonylcarbamoyl)oxy)ethyl acrylate, 2-((decylcarbamoyl)oxy)ethyl acrylate, and combinations thereof. A particularly preferred pendant carbamate monomer is 2-((butylcarbamoyl)oxy)ethyl acrylate.

[0086] In another embodiment of the present invention, the compatibilizing monomer of composition (A) is 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl and combinations thereof.Preferably, the pendant amide monomer is 2-oxo-2-(methylamino)ethyl acrylate, 2-oxo-2-(ethylamino)ethyl acrylate, 2-oxo-2-(propylamino)ethyl acrylate, 2-oxo-2-(butylamino)ethyl acrylate, 2-oxo-2-(pentylamino)ethyl acrylate, 2-oxo-2-(hexylamino)ethyl acrylate, 2-oxo-2-(heptylamino)ethyl acrylate, 2-oxo-2-(octylamino)ethyl acrylate, 2-oxo-2-(nonylamino)ethyl acrylate, 2-oxo-2-(decylamino)ethyl acrylate, 2-oxo-2-(undecylamino)ethyl acrylate, 2-oxo-2-(dodecylamino)ethyl acrylate, The alkyl acrylate is selected from 2-oxo-2-(tridecylamino)ethyl acrylate, 2-oxo-2-(tetradecylamino)ethyl acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl acrylate, 2-oxo-2-(benzylamino)ethyl acrylate, 2-oxo-2-(phenethylamino)ethyl acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl acrylate, 2-(dimethylamino)-2-oxoethyl methacrylate, and combinations thereof. More preferably, the pendant amide monomer is selected from 2-oxo-2-(methylamino)ethyl acrylate, 2-oxo-2-(ethylamino)ethyl acrylate, 2-oxo-2-(propylamino)ethyl acrylate, 2-oxo-2-(butylamino)ethyl acrylate, 2-oxo-2-(pentylamino)ethyl acrylate, 2-oxo-2-(hexylamino)ethyl acrylate, 2-oxo-2-(heptylamino)ethyl acrylate, 2-oxo-2-(octylamino)ethyl acrylate, 2-oxo-2-(nonylamino)ethyl acrylate, 2-oxo-2-(decylamino)ethyl acrylate, and combinations thereof.Most preferably, the pendant amide monomer is 2-oxo-2-(pentylamino)ethyl acrylate, 2-oxo-2-(octylamino)ethyl acrylate, 2-oxo-2-(decylamino)ethyl acrylate, and combinations thereof.

[0087] When the compatibilizing monomer in composition (A) is a mixture of pendant carbamate monomers and pendant amide monomers, a preferred mixture comprises any combination of 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, and 2-oxo-2-(decylamino)ethyl (meth)acrylate. A more preferred mixture comprises a combination of 2-((butylcarbamoyl)oxy)ethyl acrylate and 2-oxo-2-(pentylamino)ethyl acrylate.

[0088] The reactive monomer mixture of composition (A) can include the compatibilizing monomer in an amount of from about 0.01 weight percent to about 55 weight percent, from about 1 weight percent to about 40 weight percent, from about 5 weight percent to about 35 weight percent, from about 10 weight percent to about 30 weight percent, or from about 20 weight percent to about 30 weight percent.

[0089] Non-limiting examples of crosslinkers in composition (A) include tricyclo[5.2.1.0 2,6] decanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecadiodiol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, glycerol tri(meth)acrylate, triallyl cyanurate, methylene bis(meth)acrylamide, poly(ethylene glycol) di(meth)acrylate, and any combination thereof. Preferably, the crosslinker is tricyclo[5.2.1.0 2,6 ]decane dimethanol diacrylate, ethylene glycol dimethacrylate, tetraethylene dimethacrylate, and combinations thereof. More preferably, the crosslinker is selected from the group consisting of tricyclo[5.2.1.0 2,6 ] decanedimethanol di(meth)acrylate. Most preferably, the crosslinker is tricyclo[5.2.1.0 2,6 ] decanedimethanol diacrylate.

[0090] The reactive monomer mixture of composition (A) can include the crosslinker in an amount of from about 0.1 weight percent to about 10 weight percent, from about 0.1 weight percent to about 5 weight percent, from about 0.5 weight percent to about 3 weight percent, or from about 1 weight percent to about 3 weight percent.

[0091] The reactive monomer mixture of composition (A) can include ethylene glycol dicyclopentenyl ether (meth)acrylate in an amount of about 25 weight percent to about 95 weight percent, about 30 weight percent to about 75 weight percent, about 40 weight percent to about 65 weight percent, or about 45 weight percent to about 60 weight percent.

[0092] The preferred ethylene glycol dicyclopentenyl ether (meth)acrylate in composition (A) is ethylene glycol dicyclopentenyl ether acrylate.

[0093] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises an alkyl(meth)acrylate monomer, wherein the alkyl group contains 1 to 20 carbon atoms. The alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. Preferably, the alkyl(meth)acrylate is selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, 2-propyl(meth)acrylate, n-butyl(meth)acrylate, 2-butyl(meth)acrylate, tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, 2-pentyl(meth)acrylate, 3-pentyl(meth)acrylate, n-hexyl(meth)acrylate, 2-hexyl(meth)acrylate, 3-hexyl(meth)acrylate, and n-heptyl(meth). )acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-nonyl(meth)acrylate, n-decyl(meth)acrylate, n-undecyl(meth)acrylate, n-dodecyl(meth)acrylate, n-tridecyl(meth)acrylate, n-tetradecyl(meth)acrylate, n-pentadecyl(meth)acrylate, n-hexadecyl(meth)acrylate, n-heptadecyl(meth)acrylate, n-octadecylmethyl(meth)acrylate, and combinations thereof. More preferably, the alkyl (meth)acrylate is selected from n-propyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, n-undecyl acrylate, n-dodecyl acrylate, and combinations thereof. Most preferably, the alkyl (meth)acrylate is selected from n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, and combinations thereof. A particularly preferred alkyl (meth)acrylate is n-hexyl acrylate.

[0094] The reactive monomer mixture of composition (A) can include alkyl (meth)acrylate in an amount of about 0.01 to about 20 weight percent, about 1 to 20 weight percent, about 1 to about 15 weight percent, or about 1 to about 10 weight percent.

[0095] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises a hydroxyalkyl (meth)acrylate monomer, wherein the hydroxyalkyl group contains 1 to 20 carbon atoms. The hydroxyalkyl group may be a linear or branched hydroxyalkyl group. Preferably, the hydroxyalkyl (meth)acrylate is selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 1,1-dimethyl-2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-ethyl-6-hydroxyhexyl (meth)acrylate, 9-hydroxynonyl (meth)acrylate, and 10-hydroxydecyl (meth)acrylate, and combinations thereof. More preferably, the hydroxyalkyl (meth)acrylate is selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 1,1-dimethyl-2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, 7-hydroxyheptyl acrylate, 8-hydroxyoctyl acrylate, 2-ethyl-6-hydroxyhexyl acrylate, 9-hydroxynonyl acrylate, and 10-hydroxydecyl acrylate, and combinations thereof.Most preferably, the hydroxyalkyl (meth)acrylate is selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 1,1-dimethyl-2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and combinations thereof. A particularly preferred hydroxyalkyl (meth)acrylate is 4-hydroxybutyl acrylate.

[0096] The reactive monomer mixture of composition (A) can include hydroxyalkyl (meth)acrylate in an amount of about 0.01 to about 25 weight percent, about 1 to about 20 weight percent, about 5 to about 20 weight percent, or about 5 to about 15 weight percent.

[0097] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises a free-radical polymerization initiator. Some initiators thermally decompose into radicals, such as peroxides, peracids, and azo compounds. The initiation rate depends on the chemical structure of these "thermal initiators" and the polymerization temperature. Other initiators generate radicals photochemically, such as aromatic alpha-hydroxyketones, alkoxyoxybenzoins, acetophenones, monoacylphosphine oxides, and bisacylphosphine oxides. The initiation rate depends on the chemical structure of these "photoinitiators," as well as the irradiation intensity, irradiation wavelength, concentration of any inhibitors, and the level of oxygen gas in the system. Commercially available ultraviolet and / or visible light initiator systems (manufactured by IGM Resins BV, The Netherlands) include Omnirad 403, Omnirad 819, Omnirad 1173, Omnirad 1700, and Omnirad 1870. These systems and other photoinitiators that can be used are described in Volume III, Photoinitiators for Free Radical Cationic & Anionic Photopolymerization, 2nd Edition by JV Crivello & K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998.

[0098] The reactive monomer mixture of composition (A) may include a thermal initiator, a photoinitiator, or a combination thereof. Preferably, the reactive monomer mixture of composition (A) includes only a thermal initiator or only a photoinitiator. A preferred thermal initiator is azobisisobutyronitrile. Preferred photoinitiators are monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof. Most preferably, the reactive monomer mixture of composition (A) includes a bisacylphosphine oxide photoinitiator. A particularly preferred photoinitiator is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0099] The reactive monomer mixture of composition (A) can include a free radical polymerization initiator in an amount of about 0.01 weight percent to about 5 weight percent, about 0.1 weight percent to about 3 weight percent, about 0.1 weight percent to about 2 weight percent, about 0.1 weight percent to about 1 weight percent, or about 0.2 weight percent to about 0.6 weight percent. When more than one free radical polymerization initiator, including a thermal initiator, a photoinitiator, or a combination thereof, is present in the reactive monomer mixture, the above concentration ranges apply to the total amount of free radical polymerization initiator, regardless of chemical structure or means of decomposition.

[0100] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises at least one UV-absorbing compound. An exemplary UV-absorbing compound is a benzotriazole, such as 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole.

[0101] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises at least one UV / HEV absorbing compound. Preferably, the UV / HEV absorbing compound is 3-(3-(tert-butyl)-5-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenyl)propyl methacrylate. More preferably, the UV / HEV absorbing compound has the chemical structure shown in Formula V and Formula VI:

[0102] [ka] During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR 6 and X is O, S, NR, SO, or SO; Y is a linking group, P g is a polymerizable group, R 6is independently at each occurrence H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and R 4 and R 5 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted by alkyl or halo), halo, hydroxy, amino, NR 7 R 8 or benzyl, and R 7 and R 8 are independently H or C1-C6 alkyl, or two adjacent R 4 or R 5 the groups, together with the carbon atoms to which they are attached, are linked to form a cycloalkyl or aryl ring, and EWG is an electron-withdrawing group, preferably cyano;

[0103] [ka] During the ceremony, m and n are independently 0, 1, 2, 3, or 4; X is O, S, or NR 11 , SO, or SO2; R 11 is independently at each occurrence H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g Y is a linking group, and P g is a polymerizable group, R 9 and R 10 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted by alkyl or halo), halo, hydroxy, amino, NR 12 R 13 or benzyl, and R 12 and R13 are independently H or C1-C6 alkyl, or two adjacent R 9 or R 10 The groups, together with the carbon atoms to which they are attached, are linked to form a cycloalkyl or aryl ring, YP g , or TYP g and T is a bond, O, or NR 11 and EWG is an electron withdrawing group, preferably cyano.

[0104] The UV / HEV absorbing compounds of formulas V and VI preferably contain one or two YP g More preferably, the UV / HEV absorbing compound contains one YP group. g It contains a group.

[0105] The reactive monomer mixture of composition (A) can include a UV / HEV absorbing compound having a chemical structure of Formula V, such as 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(2-methoxy-10-propylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(2-methoxy-10-butylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, or any combination thereof. Preferably, the UV / HEV absorbing compound is 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate.

[0106] The reactive monomer mixture of composition (A) may include a UV / HEV absorbing compound having the chemical structure of Formula VI, preferably 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate, and the like.

[0107] The reactive monomer mixture of composition (A) can include the UV absorbing compound in an amount of about 0.01 weight percent to about 5 weight percent, about 0.05 weight percent to about 3 weight percent, about 0.1 weight percent to about 3 weight percent, about 0.1 weight percent to about 2 weight percent, about 0.1 weight percent to about 1 weight percent, or about 0.1 weight percent to about 0.5 weight percent.

[0108] The reactive monomer mixture of composition (A) can include the UV / HEV absorbing compound in an amount of about 0.01 weight percent to about 5 weight percent, about 0.05 weight percent to about 3 weight percent, about 0.1 weight percent to about 3 weight percent, about 0.1 weight percent to about 2 weight percent, about 0.1 weight percent to about 1 weight percent, or about 0.1 weight percent to about 0.5 weight percent.

[0109] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises a hydrophilic component. Preferably, the hydrophilic component is a poly(ethylene glycol)-containing monomer or macromer, depending on the number of repeating units having the chemical structure shown in Formula VII:

[0110] [ka] In the formula, R 14 is a hydrogen atom or methyl, and R 15 is selected from the group consisting of hydrogen, C1-C6 alkyl, and aryl, and "n" is an integer from 1 to 25, inclusive, including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25. Preferably, R 14 is methyl. Preferably, R 15 is a hydrogen atom, methyl, or phenyl. Preferably, "n" is an integer from 1 to 15. More preferably, "n" is an integer from 1 to 8, inclusive, including 1, 2, 3, 4, 5, 6, 7, and 8.

[0111] More preferably, the poly(ethylene glycol)-containing macromer is selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof. Most preferably, the poly(ethylene glycol)-containing macromer is selected from the group consisting of poly(ethylene glycol) methacrylate, poly(ethylene glycol) phenyl ether acrylate, and combinations thereof.

[0112] In some embodiments, the poly(ethylene glycol)-containing monomer is 200 g / mol, 220 g / mol, 240 g / mol, 260 g / mol, 280 g / mol, 300 g / mol, 320 g / mol, 340 g / mol, 360 g / mol, 380 g / mol, 400 g / mol, 420 g / mol, 440 g / mol, 460 g / mol, 480 g / mol, 500 g / mol, 520 g / mol, 540 g / mol, 560 g / mol, 580 g / mol, 600 g / mol mol, 620 g / mol, 640 g / mol, 660 g / mol, 680 g / mol, 700 g / mol, 720 g / mol, 740 g / mol, 760 g / mol, 780 g / mol, 800 g / mol, 820 g / mol, 840 g / mol, 860 g / mol, 880 g / mol, 900 g / mol, 920 g / mol, 940 g / mol, 960 g / mol, 980 g / mol, and 1000 g / mol. n In some embodiments, the poly(ethylene glycol)-containing monomer has a number average molecular weight (M) of about 200 g / mol to about 400 g / mol, including 200 g / mol, 220 g / mol, 240 g / mol, 260 g / mol, 280 g / mol, 300 g / mol, 320 g / mol, 340 g / mol, 360 g / mol, 380 g / mol, and 400 g / mol. n )

[0113] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises a cycloalkyl(alkyl)(meth)acrylate. Preferred cycloalkyl(alkyl)(meth)acrylates are cyclohexylmethyl acrylate, 2-cyclohexylethyl acrylate, and 3-cyclohexylpropyl acrylate.

[0114] In some embodiments of the present invention, the reactive monomer mixture of composition (A) further comprises at least one diluent. Any organic solvent can be used to dissolve the components of the reactive monomer mixture. Preferably, the organic solvent is also selected so that it is extractable from composition (A) after the free radical polymerization is complete and has a boiling point sufficiently higher than the polymerization temperature to avoid the formation of bubbles and cavitation.

[0115] In some embodiments of the present invention, composition (A) exhibits the following refractive index and Abbe number combinations: (a) a refractive index of at least 1.45 and an Abbe number of at least 45; (b) a refractive index of at least 1.48 and an Abbe number of at least 48; (c) a refractive index of at least 1.49 and an Abbe number of at least 49; (d) a refractive index of at least 1.50 and an Abbe number of at least 50; (e) a refractive index of at least 1.51 and an Abbe number of at least 51; or (f) a refractive index of at least 1.52 and an Abbe number of at least 52.

[0116] In some embodiments of the present invention, composition (A) exhibits a water content of about 0.01 weight percent to about 15 weight percent, about 0.1 weight percent to about 10 weight percent, about 0.5 weight percent to about 5 weight percent, about 0.5 weight percent to about 3 weight percent, or about 1 weight percent to about 2 weight percent. A preferred water content is about 1 weight percent to about 2 weight percent.

[0117] In some embodiments of the present invention, composition (A) exhibits a storage modulus of about 1 MPa to about 100 MPa, about 10 MPa to about 90 MPa, about 20 MPa to about 80 MPa, about 30 MPa to about 80 MPa, or about 40 MPa to about 80 MPa. A preferred storage modulus is about 40 MPa to about 80 MPa.

[0118] In certain embodiments of the invention, the reactive monomer mixture comprises 24 to 28 weight percent 2-((butylcarbamoyl)oxy)ethyl acrylate; 10 weight percent 4-hydroxybutyl acrylate; 1.5 weight percent tricyclo[5.2.1.0]methylpropanol; 2,6 0.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 55 to 59 weight percent ethylene glycol dicyclopentenyl ether acrylate; and 3 to 6 weight percent n-hexyl acrylate, wherein the concentrations of ethylene glycol dicyclopentenyl ether acrylate and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and a storage modulus of 1 megapascal to 100 megapascals ["Composition (B)"].

[0119] In another particular embodiment of the invention, the reactive monomer mixture comprises 16 to 18 weight percent 2-oxo-2-(decylamino)ethyl (meth)acrylate; 10 weight percent 4-hydroxybutyl acrylate; 1.5 weight percent tricyclo[5.2.1.0]methylpropanol; 2,60.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 65 to 67 weight percent ethylene glycol dicyclopentenyl ether acrylate; and 5 to 7 weight percent n-hexyl acrylate, wherein the concentrations of 2-oxo-2-(decylamino)ethyl (meth)acrylate, ethylene glycol dicyclopentenyl ether acrylate, and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and a storage modulus of 1 megapascal to 100 megapascals ["Composition (C)"].

[0120] Another aspect of the present invention is a compound of formula II, P g -L-CONR 1 R 2 wherein P g is a polymerizable group, L is a linking group, and R 1 and R 2 are independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups ["Compound (A)"]. Compound (A) is a pendant amide monomer.

[0121] Non-limiting examples of the polymerizable group of compound (A) include (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, styrene, vinyl ether, O-vinyl carbamate, O-vinyl carbonate, and other vinyl groups. Preferably, the polymerizable group comprises a (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide group, or a mixture thereof. More preferably, the polymerizable group comprises a (meth)acrylate, (meth)acrylamide, or a combination thereof. Most preferably, the polymerizable group comprises a (meth)acrylate.

[0122] Non-limiting examples of the linking group of compound (A) include alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, ester, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, and haloalkyleneoxy. Preferred linking groups include ester, amide, C1-C8 alkylene, C1-C8 oxaalkylene, C1-C8 alkylene-ester-C1-C8 alkylene, and C1-C8 alkylene-amido-C1-C8 alkylene. More preferred linking groups include C1-C8 alkylene and C1-C8 oxaalkylene. Most preferred linking groups include C1-C8 alkylene. A particularly preferred linking group is unsubstituted C1-C4 alkylene.

[0123] In some embodiments of the present invention, compounds (A) having a combination of a (meth)acrylate polymerizable group and an unsubstituted alkylene linking group are preferred. In particular, compounds (A) having the chemical structure shown in Formula IV are most preferred:

[0124] [ka] In the formula, R 1 and R 2is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; R 3 is H or methyl.

[0125] Non-limiting examples of compound (A) having the chemical structure of formula IV include 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-( 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecyl amino)ethyl (meth)acrylate, 2-oxo-2-(tridecylamino)ethyl (meth)acrylate, 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl acrylate, and 2-(dimethylamino)-2-oxoethyl methacrylate.

[0126] In some aspects of the present invention, the presently disclosed subject matter provides compositions made by free radical polymerization of a reactive monomer mixture, the reactive monomer mixture comprising: (a) a pendant amide monomer having the chemical structure of Formula IV

[0127] [ka] In the formula, R 1 and R 2 is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; R 3 is H or methyl ["Composition (D)"].

[0128] Non-limiting examples of pendant amide monomers having the chemical structure of Formula IV include 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo -2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(do 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(tridecylamino)ethyl (meth)acrylate, 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl

[0033] Examples of suitable methacrylates include 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl acrylate, and 2-(dimethylamino)-2-oxoethyl methacrylate.

[0129] In some embodiments of the present invention, the reactive monomer mixture of composition (D) further comprises additional components selected from the group consisting of hydrophilic components, silicone-containing components, alkyl(meth)acrylates, hydroxyalkyl(meth)acrylates, cycloalkyl(alkyl)(meth)acrylates, polyamides, UV absorbing compounds, UV / HEV absorbing compounds, visible dyes, crosslinkers, free radical polymerization initiators, and diluents. These additional components are either defined herein or broadly disclosed in U.S. Pat. No. 10,935,695, which is incorporated herein by reference in its entirety.

[0130] C. Ophthalmic Devices In some aspects of the present invention, the presently disclosed subject matter provides a device comprising the compositions just described, i.e., composition (A), composition (B), composition (C), and composition (D).

[0131] In another aspect, the device comprises an ophthalmic lens, inlay, outlay, implant, or insert selected from an intraocular implant, an intraocular lens, a phakic intraocular lens, a contact lens, an orthokeratology lens, a rigid gas permeable lens, a corneal inlay, a corneal outlay, and a corneal insert. In yet another aspect of the present invention, the above-described ophthalmic device can be coated after manufacture to modify the surface properties of the lens or implant. Any coating method can be used, including, but not limited to, dip coating, spray coating, spin coating, chemical vapor deposition, sALD, plasma treatment, and the like. The coating methodology can also include a curing step using any known chemistry, such as photochemical polymerization, to create a robust coating.

[0132] In certain embodiments, the ophthalmic device is an intraocular lens or implant. More specifically, the presently disclosed subject matter provides intraocular implants and / or lenses made at least partially or completely from the compositions described herein. Such intraocular implants or lenses can include an optic and one or more haptics. Typically, the composition of the presently disclosed subject matter constitutes part or all of the optic of the intraocular implant or lens. In some embodiments, the optic of the implant or lens has a core made from one of the compositions described herein surrounded by a different polymer or material. Implants or lenses whose optic is made at least in part from one of the compositions of the presently disclosed subject matter also typically have haptics. The haptics can also be made from the polymer of the present disclosure or can be made from a different material, such as another polymer.

[0133] In yet another aspect, the intraocular implant or lens of the presently disclosed subject matter is a monolithic lens having a soft, foldable central optic region and peripheral regions (haptics) where both regions are made of the same polymer. In other embodiments, the optic and haptics regions can be formed from different types of polymers or materials, as needed. Some implants or lenses can also have haptics composed of different materials, e.g., one or more haptics made from the same material as the optic and other haptics made from a material other than the polymer of the present disclosure. Multi-component implants or lenses can be made by embedding one material with the other in a coextrusion process, solidifying a hard material around a soft material, or forming an interpenetrating network of hard components around a preformed hydrophobic core. When one or more haptics are made from a different material than the optic of the lens, the haptics can be attached to the optic by any method known in the art, such as by drilling a hole or holes in the optic and inserting the haptics.

[0134] The compositions described herein are designed to be foldable so that intraocular lenses can be inserted into an individual's eye through a small incision. In some instances, the incision is less than 2.5 millimeters in diameter, and in some instances, the incision is less than 2 millimeters in diameter. The haptics of the lens provide the necessary support for the implant or lens within the eye after insertion and deployment of the lens, and tend to help stabilize the position of the lens after insertion and the closure of the incision. The shape of the haptics design is not particularly limited and may be any desired configuration, such as a plate-shaped or graduated thickness spiral filament, also known as a C-loop design.

[0135] The optic portion of the intraocular lens may be approximately 2-6 mm in diameter before hydration. A diameter of 2-6 mm is fairly standard in the art and is generally selected to cover a fully dilated pupil under naturally occurring conditions. However, other sizes are contemplated, and the subject matter of the present disclosure is not limited to any particular diameter or size of the intraocular lens. Furthermore, the lens optic portion need not be circular, but may be oval, square, or any other shape, as desired.

[0136] The intraocular lens may further include one or more non-optical haptics extending away from the outermost periphery of the optic portion. The haptics may be of any desired shape, such as graduated spiral filaments or flat sections, and are used to support the lens in the posterior chamber. Lenses having any desired design configuration may be fabricated. Should the intraocular lens include other components besides the optic and haptics, such other components may be made of polymers, like the haptics and optic portions, or of other materials as needed.

[0137] The intraocular implant lens can be inserted into the eye by any method known in the art. For example, the intraocular lens may be folded before insertion into the eye using an intraocular lens inserter or with small, thin forceps of the type typically used by ophthalmic surgeons. After the implant or lens is positioned at the desired location, it is released and unfolded. As known in the art, a replacement lens is typically removed before inserting the intraocular lens. The intraocular lenses of the presently disclosed subject matter can be made of soft, generally physiologically inert polymeric materials that can provide a clear, transparent refractive lens body even after folding and unfolding. In some embodiments, the foldable intraocular lenses of the presently disclosed subject matter can be inserted into any eye by injection, whereby the mechanically compatible material is folded and forced into a small tube, such as a tube with an inner diameter of 1 to 3 millimeters.

[0138] Other embodiments of the present invention exist in which monomers having the chemical structure of Formula IV are used to manufacture contact lenses, including, but not limited to, soft hydrogel contact lenses, soft silicone hydrogel contact lenses, hard contact lenses, rigid gas permeable lenses, and orthokeratological lenses. A further embodiment of the present invention includes the preparation of reactive monomer mixture components from monomers having the chemical structure of Formula IV, including, but not limited to, internal wetting agents and plasticizers. Another embodiment of the present invention includes the preparation of packaging solution additives, such as polymeric comfort agents, from monomers having the chemical structure of Formula IV.

[0139] D. Methods for Manufacturing Ophthalmic Devices In yet another embodiment, the presently disclosed subject matter provides a method for making an ophthalmic device, the method comprising: (a) providing any of the compositions described herein (e.g., composition (A), composition (B), composition (C), or composition (D)); and (b) forming an ophthalmic device. In another embodiment, the presently disclosed subject matter provides a method for manufacturing an ophthalmic device, the method comprising: (a) preparing a sample from any of the compositions described herein (e.g., composition (A), composition (B), composition (C), or composition (D)); and (b) machining an ophthalmic device from the sample. The sample may be any shape or size, but typically has a circular or rectangular cross-section. Preferred samples are circular disks. In yet another embodiment, the presently disclosed subject matter provides a method for manufacturing an ophthalmic device, the method comprising molding an ophthalmic device from any of the compositions described herein (e.g., composition (A), composition (B), composition (C), or composition (D)). Alternatively, the method includes (a) providing any of the compositions described herein (e.g., composition (A), composition (B), composition (C), or composition (D)) in a mold assembly, (b) forming an ophthalmic device by a photopolymerization reaction, and (c) removing the ophthalmic device from the mold assembly. Alternatively, the method includes (a) providing any of the compositions described herein (e.g., composition (A), composition (B), composition (C), or composition (D)) in a mold assembly, (b) forming an ophthalmic device by a thermal polymerization reaction, and (c) removing the ophthalmic device from the mold assembly. In yet other embodiments, the presently disclosed subject matter provides a method for manufacturing an ophthalmic device, the method including molding an ophthalmic device from any of the compositions described herein (e.g., composition (A), composition (B), composition (C), or composition (D)) and then granulating the surface by lathing. In certain embodiments of any of the methods, the method further includes extracting the ophthalmic device with a solvent. In certain embodiments, the method further comprises hydrating the extracted ophthalmic device with at least one aqueous solution.In certain embodiments, the method further comprises irradiating using a laser, and in certain embodiments, the laser is a two-photon laser, and in more particular embodiments, a femtosecond two-photon laser. In more particular embodiments, the method further comprises sterilizing the ophthalmic device. Ophthalmic devices can be sterilized by known means, including, but not limited to, high-pressure steam treatment and exposure to ethylene oxide gas.

[0140] The present invention provides a method for manufacturing an ophthalmic device, the method comprising: (a) providing a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate; and (b) forming an ophthalmic device; alternatively, (a) molding a device from a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate; alternatively, (a) providing a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate in a mold assembly; (b) forming an ophthalmic device; and (c) removing the ophthalmic device from the mold assembly; alternatively, (a) providing a composition comprising a compatibilizing monomer, a crosslinking agent, and ethylene glycol dicyclopentenyl ether (meth)acrylate in a mold assembly; (b) forming an ophthalmic device by a photopolymerization reaction; and (c) removing the ophthalmic device from the mold assembly. In certain aspects of any of the aforementioned methods for manufacturing an ophthalmic device, the method further comprises extracting the ophthalmic device with a solvent. In certain aspects of any of the aforementioned methods for manufacturing an ophthalmic device, the method further comprises hydrating the extracted ophthalmic device with at least one aqueous solution. In yet other aspects of any of the aforementioned methods for manufacturing an ophthalmic device, the method further comprises sterilizing the ophthalmic device. The ophthalmic device may be sterilized by known means, such as, but not limited to, high-pressure steam treatment and exposure to ethylene oxide gas. In certain embodiments of any of the aforementioned methods for manufacturing an ophthalmic device, the method further comprises an irradiation step using a laser either before or after sterilization, including after the ophthalmic device has been implanted in a human. The laser may be, but is not limited to, a two-photon laser, such as a femtosecond two-photon laser. In certain embodiments of any of the aforementioned methods for manufacturing an ophthalmic device, the method further comprises a coating step in which the formed device is coated using any coating methodology, including, but not limited to, dip coating, spray coating, spin coating, chemical vapor deposition, plasma treatment, sALD, etc.The coating methodology may also include a curing step by any known chemistry, such as photochemical polymerization, to create a robust coating.

[0141] Another specific aspect of the present invention relating to any method of manufacturing an ophthalmic device from the compositions disclosed herein, including composition (A), composition (B), composition (C), and composition (D), is a forming or molding step that includes a photopolymerization reaction that includes irradiating the mold assembly from the top and bottom with 435 nanometer light emitting diodes, the light emitting diodes having the following intensity profile: 5 mW / cm 2 for 20 minutes (2.5 mW / cm 2 Top and 2.5mW / cm 2 bottom), 10mW / cm 2 for 20 minutes (5 mW / cm 2 Top and 5mW / cm 2 bottom), 20mW / cm 2 for 20 minutes (10 mW / cm 2 Top and 10mW / cm 2 bottom), and 30 mW / cm 2 for 30 minutes (15 mW / cm 2 Top and 15mW / cm 2 bottom).

[0142] Yet another specific aspect of the present invention relating to any method of manufacturing an ophthalmic device from the compositions disclosed herein, including composition (A), composition (B), composition (C), and composition (D), is a solvent extraction process comprising a solvent selected from the group consisting of acetonitrile, isopropanol, and an aqueous solution of acetonitrile or isopropanol.

[0143] In another embodiment of the present invention, a compound having the chemical structure of Formula IV can be prepared by a process comprising: (a) reacting a primary or secondary amine with methyl glycolate to form an N-alkyl-2-hydroxyacetamide or an N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide; and (b) reacting the N-alkyl-2-hydroxyacetamide or the N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide with (meth)acryloyl chloride.

[0144] item Certain aspects of the invention described herein can be combined in whole or in part. The following clauses list some non-limiting embodiments of the present disclosure.

[0145] Clause 1. A composition prepared by free radical polymerization of a reactive monomer mixture, comprising: a) a compatibilizing monomer selected from the group consisting of a pendant carbamate monomer having a chemical structure of Formula I, a pendant amide monomer having a chemical structure of Formula II, and combinations thereof; P g -L-OCONR 1 R 2 Formula I P g -L-CONR 1 R 2 Formula II, In the formula, P g is a polymerizable group, L is a linking group, and R 1 and R 2is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; a crosslinker; and ethylene glycol dicyclopentenyl ether (meth)acrylate, wherein the concentration of ethylene glycol dicyclopentenyl ether (meth)acrylate in the reactive monomer mixture, excluding any diluent, is 20 weight percent or greater, and the composition exhibits a refractive index of at least 1.45 and an Abbe number of at least 39.

[0146] Clause 2. The composition of clause 1, wherein the polymerizable group of the compatibilizing monomer is a (meth)acrylate and the linking group of the compatibilizing monomer is an unsubstituted alkylene group.

[0147] Clause 3. The compatibilizing monomer is selected from the group consisting of Formula III, Formula IV, and combinations thereof:

[0148] [ka] In the formula, R 3 is H or methyl.

[0149] Clause 4. The compatibilizing monomer is 2-((methylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((ethylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((propylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((hexylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptylcarbamoyl)oxy)ethyl (meth)acrylate, 2-( (Octylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((nonylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((decylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((undecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((dodecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tridecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tetradecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentadecylcarbamoyl) 2-((hexadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl (meth)acrylate, 2-oxo-2-(tridecylamino)ethyl (meth)acrylate,4. The composition of clause 3, wherein the methyl group is selected from the group consisting of 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl (meth)acrylate, 2-(dimethylamino)-2-oxoethyl methacrylate, and combinations thereof.

[0150] Clause 5. The composition of clause 4, wherein the compatibilizing monomer is selected from the group consisting of 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, and combinations thereof.

[0151] Clause 6. The composition of clause 5, wherein the compatibilizing monomer is selected from the group consisting of 2-((butylcarbamoyl)oxy)ethyl acrylate, 2-oxo-2-(pentylamino)ethyl acrylate, and combinations thereof.

[0152] Article 7. The crosslinker is tricyclo[5.2.1.0 2,6]Decanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecadiodiol di(meth)acrylate 7. The composition of any one of clauses 1 to 6, wherein the diol is selected from the group consisting of 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, glycerol tri(meth)acrylate, triallyl cyanurate, methylene bis(meth)acrylamide, poly(ethylene glycol) di(meth)acrylate, and any combination thereof.

[0153] Article 8. The crosslinker is tricyclo[5.2.1.0 2,6 8. The composition of claim 7, wherein the acrylate is selected from the group consisting of decanedimethanol diacrylate, ethylene glycol dimethacrylate, and combinations thereof.

[0154] Article 9. The crosslinker is tricyclo[5.2.1.0 2,6 9. The composition of claim 8, wherein the compound is decanedimethanol diacrylate.

[0155] Clause 10. The composition according to any one of clauses 1 to 9, wherein the ethylene glycol dicyclopentenyl ether (meth)acrylate is ethylene glycol dicyclopentenyl ether acrylate.

[0156] Clause 11. The composition of any one of clauses 1 to 10, further comprising an aliphatic alkyl (meth)acrylate monomer, wherein the alkyl group contains 1 to 20 carbon atoms.

[0157] Clause 12. The composition according to clause 11, wherein the aliphatic alkyl (meth)acrylate is n-hexyl acrylate.

[0158] Clause 13. The composition of clause 12, wherein the reactive monomer mixture comprises n-hexyl acrylate in an amount of about 0.01 to about 20 weight percent, about 1 weight percent to 20 weight percent, about 1 weight percent to about 15 weight percent, or about 1 weight percent to about 10 weight percent.

[0159] Clause 14. The composition of any one of clauses 1 to 13, further comprising a hydroxyalkyl (meth)acrylate monomer, wherein the hydroxyalkyl group contains 1 to 20 carbon atoms.

[0160] Clause 15. The composition of clause 14, wherein the hydroxyalkyl (meth)acrylate monomer is 4-hydroxybutyl acrylate.

[0161] Clause 16. The composition of clause 15, wherein the reactive monomer mixture comprises 4-hydroxybutyl acrylate in an amount of about 0.01 to about 25 weight percent, about 1 weight percent to about 20 weight percent, about 5 weight percent to about 20 weight percent, or about 5 weight percent to about 15 weight percent.

[0162] Clause 17. The composition of any one of clauses 1 to 16, further comprising a free radical polymerization initiator.

[0163] Clause 18. The composition of clause 17, wherein the free radical polymerization initiator is a photoinitiator.

[0164] Clause 19. The composition of clause 18, wherein the photoinitiator is a bisacylphosphine oxide initiator.

[0165] Clause 20. The composition of clause 19, wherein the bisacylphosphine oxide initiator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0166] Clause 21. The composition of any one of clauses 17-20, wherein the reactive monomer mixture comprises a free radical polymerization initiator in an amount of about 0.01 weight percent to about 5 weight percent, about 0.1 weight percent to about 3 weight percent, about 0.1 weight percent to about 2 weight percent, about 0.1 weight percent to about 1 weight percent, or about 0.2 weight percent to about 0.6 weight percent.

[0167] Clause 22. The composition of any one of clauses 1 to 21, wherein the reactive monomer mixture further comprises at least one UV absorbing compound.

[0168] Clause 23. The composition of any one of clauses 1 to 22, wherein the reactive monomer mixture further comprises at least one UV / HEV absorbing compound.

[0169] Clause 24. The composition of clause 23, wherein the UV / HEV absorbing compound is selected from the group consisting of 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate, 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 3-(3-(tert-butyl)-5-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenyl)propyl methacrylate, or any combination thereof.

[0170] Clause 25. The composition of clause 24, wherein the UV / HEV absorbing compound is 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate.

[0171] Clause 26. The composition of any one of clauses 23-25, wherein the reactive monomer mixture comprises a UV / HEV absorbing compound in an amount of about 0.01 weight percent to about 5 weight percent, about 0.05 weight percent to about 3 weight percent, about 0.1 weight percent to about 3 weight percent, about 0.1 weight percent to about 2 weight percent, about 0.1 weight percent to about 1 weight percent, or about 0.1 weight percent to about 0.5 weight percent.

[0172] Clause 27. The composition of any one of clauses 1 to 26, further comprising a hydrophilic component selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof.

[0173] Clause 28. The composition of clause 27, wherein the hydrophilic component is selected from the group consisting of poly(ethylene glycol) methacrylate, poly(ethylene glycol) phenyl ether acrylate, and combinations thereof.

[0174] Clause 29. The composition of any one of clauses 1-28, wherein the reactive monomer mixture comprises a compatibilizing monomer in an amount of about 0.01 weight percent to about 55 weight percent, about 1 weight percent to about 40 weight percent, about 5 weight percent to about 35 weight percent, about 10 weight percent to about 30 weight percent, or about 20 weight percent to about 30 weight percent.

[0175] Clause 30. The composition of any one of clauses 1 to 29, wherein the reactive monomer mixture comprises a crosslinker in an amount of about 0.1 weight percent to about 10 weight percent, about 0.1 weight percent to about 5 weight percent, about 0.5 weight percent to about 3 weight percent, or about 1 weight percent to 3 weight percent.

[0176] Clause 31. The composition of any one of clauses 1 to 30, wherein the reactive monomer mixture comprises ethylene glycol dicyclopentenyl ether (meth)acrylate in an amount of about 25 weight percent to about 95 weight percent, about 30 weight percent to about 75 weight percent, about 40 weight percent to about 65 weight percent, or about 45 weight percent to about 60 weight percent.

[0177] Clause 32. The composition of any one of clauses 1 to 31, wherein the reactive monomer mixture further comprises at least one diluent.

[0178] Clause 33. The composition of any one of clauses 1 to 32, wherein the composition has a refractive index of at least 1.45 and an Abbe number of at least 45; wherein the composition has a refractive index of at least 1.48 and an Abbe number of at least 48; wherein the composition has a refractive index of at least 1.49 and an Abbe number of at least 49; wherein the composition has a refractive index of at least 1.50 and an Abbe number of at least 50; wherein the composition has a refractive index of at least 1.51 and an Abbe number of at least 51; or wherein the composition has a refractive index of at least 1.52 and an Abbe number of at least 52.

[0179] Clause 34. The composition of any one of clauses 1 to 33, wherein the composition exhibits a water content of from about 0.01 weight percent to about 15 weight percent, from about 0.1 weight percent to about 10 weight percent, from about 0.5 weight percent to about 5 weight percent, from about 0.5 weight percent to about 3 weight percent, or from about 1 weight percent to about 2 weight percent.

[0180] Clause 35. The composition of any one of clauses 1 to 34, wherein the composition exhibits a storage modulus of about 1 MPa to about 100 MPa, about 10 MPa to about 90 MPa, about 20 MPa to about 80 MPa, about 30 MPa to about 80 MPa, or about 40 MPa to about 80 MPa.

[0181] Clause 36. An ophthalmic device comprising the composition of any one of clauses 1 to 35.

[0182] Clause 37. The ophthalmic device of Clause 36, wherein the ophthalmic device comprises an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert.

[0183] Clause 38. An ophthalmic device according to Clause 37, wherein the ophthalmic device is an intraocular lens.

[0184] Clause 39. An ophthalmic device according to clause 38, wherein the intraocular lens is coated.

[0185] Clause 40. A method for manufacturing an ophthalmic device, the method comprising providing a composition according to any one of clauses 1 to 35 and forming an ophthalmic device.

[0186] Clause 41. A method for manufacturing an ophthalmic device, the method comprising preparing a blank from the composition of any one of clauses 1 to 35, and machining an ophthalmic device from the blank.

[0187] Clause 42. A method for manufacturing an ophthalmic device, comprising molding the device from the composition of any one of clauses 1 to 35.

[0188] Clause 43. A method for manufacturing an ophthalmic device, the method comprising providing the composition of any one of clauses 1-35 in a mold assembly, forming an ophthalmic device, and removing the ophthalmic device from the mold assembly.

[0189] Clause 44. A method for manufacturing an ophthalmic device, the method comprising providing the composition of any one of clauses 1-35 in a mold assembly, forming an ophthalmic device by photopolymerization, and removing the ophthalmic device from the mold assembly.

[0190] Clause 45. The photopolymerization reaction includes irradiating the mold assembly from the top and bottom with 435 nanometer light emitting diodes, the light emitting diodes having an intensity profile of 5 mW / cm. 2 for 20 minutes (2.5 mW / cm 2 Top and 2.5mW / cm 2 bottom), 10mW / cm 2 for 20 minutes (5 mW / cm 2 Top and 5mW / cm 2 bottom), 20mW / cm 2 for 20 minutes (10 mW / cm 2 Top and 10mW / cm 2 bottom), and 30 mW / cm2 for 30 minutes (15 mW / cm 2 Top and 15mW / cm 2 45. The method of claim 44, having a bottom.

[0191] Clause 46. The method of any one of clauses 39 to 45, further comprising extracting the ophthalmic device with a solvent.

[0192] Clause 47. The method of clause 46, wherein the solvent is selected from the group consisting of acetonitrile, isopropanol, and an aqueous solution of acetonitrile or isopropanol.

[0193] Clause 48. The method of any one of clauses 40 to 47, further comprising the step of hydrating the extracted ophthalmic device with at least one aqueous solution.

[0194] Clause 49. The method of any one of clauses 40 to 48, further comprising the step of sterilizing the ophthalmic device.

[0195] Clause 50. The method of clause 49, further comprising irradiating the ophthalmic device using a femtosecond two-photon laser either before or after sterilization.

[0196] Clause 51. The method of clause 50, wherein the irradiating step is performed on an implanted ophthalmic device.

[0197] Clause 52. The method of any one of clauses 40 to 51, wherein the ophthalmic device is selected from the group consisting of an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert.

[0198] Clause 53. The method of clause 52, wherein the ophthalmic device is an intraocular lens.

[0199] Clause 54. A composition prepared by free radical polymerization of a reactive monomer mixture, the reactive monomer mixture comprising 24 to 28 weight percent 2-((butylcarbamoyl)oxy)ethyl acrylate; 10 weight percent 4-hydroxybutyl acrylate; 1.5 weight percent tricyclo[5.2.1.0] 2,6 0.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 55 to 59 weight percent ethylene glycol dicyclopentenyl ether acrylate; and 4 to 6 weight percent n-hexyl acrylate, wherein the concentrations of ethylene glycol dicyclopentenyl ether acrylate and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and a storage modulus of 1 megapascal to 100 megapascals.

[0200] Clause 55. A composition prepared by free radical polymerization of a reactive monomer mixture, the reactive monomer mixture comprising 16 to 18 weight percent 2-oxo-2-(decylamino)ethyl (meth)acrylate; 10 weight percent 4-hydroxybutyl acrylate; 1.5 weight percent tricyclo[5.2.1.0] 2,60.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 65 to 67 weight percent ethylene glycol dicyclopentenyl ether acrylate; and 5 to 7 weight percent n-hexyl acrylate, wherein the concentrations of 2-oxo-2-(decylamino)ethyl (meth)acrylate, ethylene glycol dicyclopentenyl ether acrylate, and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and a storage modulus of 1 megapascal to 100 megapascals.

[0201] Clause 56. An ophthalmic device manufactured from the composition according to any one of clauses 54-55.

[0202] Clause 57. An ophthalmic device according to Clause 56, wherein the ophthalmic device is an intraocular lens.

[0203] Clause 58. An ophthalmic device according to clause 57, wherein the intraocular lens is coated.

[0204] Article 59. Formula II, P g -L-CONR 1 R 2 wherein P g is a polymerizable group, L is a linking group, and R 1 and R 2 are independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups.

[0205] Clause 60. The compound according to clause 59, wherein the polymerizable group is a (meth)acrylate and the linking group is an unsubstituted alkylene group.

[0206] Article 61. The compound has a chemical structure represented by formula IV:

[0207] [ka] In the formula, R 3 61. The compound according to any one of clauses 59-60, wherein is H or methyl.

[0208] Clause 62. The compound is 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 62. The compound of clause 61, wherein the compound is selected from the group consisting of 2-oxo-2-(tridecylamino)ethyl (meth)acrylate, 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl acrylate, and 2-(dimethylamino)-2-oxoethyl methacrylate.

[0209] Clause 63. A method for making any of the compounds of clauses 59-62, comprising: (a) reacting a primary or secondary amine with methyl glycolate to form an N-alkyl-2-hydroxyacetamide or an N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide; and (b) reacting the N-alkyl-2-hydroxyacetamide or the N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide with (meth)acryloyl chloride.

[0210] Clause 64. A composition prepared by free radical polymerization of a reactive monomer mixture comprising any of the compounds described in clauses 59-62.

[0211] Article 65. The reactive monomer mixture is a) a cross-linking agent; and b) ethylene glycol dicyclopentenyl ether (meth)acrylate; c) aliphatic alkyl (meth)acrylate monomers; d) hydroxyalkyl (meth)acrylate monomers; e) free radical polymerization initiators; f) at least one UV absorbing compound; g) at least one UV / HEV absorbing compound; h) a hydrophilic component selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof; and i) at least one diluent.

[0212] Clause 66. An ophthalmic device comprising any of the compositions described in clauses 64-65.

[0213] Clause 67. The ophthalmic device of Clause 66, wherein the ophthalmic device is selected from the group consisting of an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert.

[0214] Clause 68. An ophthalmic device according to Clause 67, wherein the ophthalmic device is a contact lens.

[0215] Clause 69. A hydrogel composition prepared by free radical polymerization of a reactive monomer mixture, the reactive monomer mixture having Formula II, P g -L-CONR 1 R 2 A monomer having the chemical structure: g is a polymerizable group, L is a linking group, and R 1 and R 2 are independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups, a crosslinker, and an initiator, wherein the hydrogel composition has a water content of 10 weight percent to 90 weight percent, 20 weight percent to 75 weight percent, or 30 weight percent to 65 weight percent.

[0216] Clause 70. The polymerizable group is a (meth)acrylate, the linking group is an alkylene group, and R 1 and R 2 is independently selected from H, alkyl, alkoxyalkyl, and hydroxyalkyl.

[0217] Article 71. The monomer has the chemical structure shown in formula IV:

[0218] [ka] In the formula, R 371. The hydrogel composition of clause 70, wherein is H or methyl.

[0219] Clause 71. The hydrogel composition of any one of clauses 69 to 71, further comprising a hydrophilic component.

[0220] Clause 72. The hydrogel composition of clause 71, wherein the hydrophilic component is selected from the group consisting of N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA), N-vinylmethacetamide (VMA), and N-vinylN-methylacetamide (NVA).

[0221] Clause 73. The hydrogel composition of any one of clauses 69-72, further comprising a silicone-containing component, thereby forming a silicone hydrogel composition.

[0222] Clause 74. The silicone-containing component has a chemical structure of formula A:

[0223] [ka] wherein at least one R A is the formula P g -L- group, where P g is a polymerizable group, L is a linking group, and the remaining R A are each independently j)P g -L-, k) C1-C optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 16 Alkyl, l) C3-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 12cycloalkyl, m) C6-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 14 aryl, n) halo, o) alkoxy, cyclic alkoxy, or aryloxy; p) siloxy, q) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as polyethyleneoxyalkyl, polypropyleneoxyalkyl, or poly(ethyleneoxy-co-propyleneoxyalkyl), or r) a monovalent siloxane chain comprising 1 to 100 siloxane repeat units optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxy, alkylcarboxy, alkoxy, amido, carbamate, halo, or combinations thereof; 74. The hydrogel composition of clause 73, wherein n is 0 to 500, or 0 to 200, or 0 to 100, or 0 to 20, and when n is other than 0, n is a distribution having a mode equal to the recited value, and when n is 2 or greater, it is understood that the SiO units may have the same or different R A substituents, and when different R A substituents are present, the n groups may be in a random or block configuration.

[0224] Clause 75. The hydrogel composition of clause 74, wherein the silicone-containing component is selected from the group consisting of mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane (mPDMS), mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminated polydimethylsiloxane (OH-mPDMS), 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate (SiMAA), and 3-(3-(1,5-di-tert-butyl-1,1,3,5,5-pentamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate (tBu-SiMAA).

[0225] Clause 76. The hydrogel composition of any one of clauses 69 to 75, further comprising a polyamide.

[0226] Clause 77. The hydrogel composition of clause 76, wherein the polyamide is selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), and combinations thereof.

[0227] Clause 78. The hydrogel composition of any one of clauses 69 to 77, further comprising an ultraviolet light absorbing compound.

[0228] Clause 79. The hydrogel composition of Clause 78, wherein the ultraviolet light absorbing compound is 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole.

[0229] Clause 80. The hydrogel composition of any one of clauses 69 to 79, further comprising a UV / HEV absorbing compound.

[0230] Article 81. The UV-HEV absorbing compound has the chemical structure shown in Formula V and Formula VI:

[0231] [ka] During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR 6 and X is O, S, NR, SO, or SO; Y is a linking group, P g is a polymerizable group, R 6 is independently at each occurrence H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and R 4 and R 5 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted by alkyl or halo), halo, hydroxy, amino, NR 7 R 8 or benzyl, and R 7 and R 8 are independently H or C1-C6 alkyl, or two adjacent R 4 or R 5 the groups, together with the carbon atoms to which they are attached, are linked to form a cycloalkyl or aryl ring, and EWG is an electron-withdrawing group, preferably cyano;

[0232] [ka] During the ceremony, m and n are independently 0, 1, 2, 3, or 4; X is O, S, or NR 11 , SO, or SO2; R 11 is independently at each occurrence H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g Y is a linking group, and Pg is a polymerizable group, R 9 and R 10 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted by alkyl or halo), halo, hydroxy, amino, NR 12 R 13 or benzyl, and R 12 and R 13 are independently H or C1-C6 alkyl, or two adjacent R 9 or R 10 The groups, together with the carbon atoms to which they are attached, are linked to form a cycloalkyl or aryl ring, YP g , or TYP g and T is a bond, O, or NR 11 81. The hydrogel composition of clause 80, wherein EWG is an electron withdrawing group, preferably cyano.

[0233] Clause 80. The UV / HEV absorbing compound is selected from the group consisting of 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(2-methoxy-10-propyl 80. The hydrogel composition of clause 79, wherein the compound is selected from the group consisting of 2-(2-cyano-2-(2-methoxy-10-butylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(2-methoxy-10-butylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate, or any combination thereof.

[0234] Clause 81. The hydrogel composition of any one of clauses 69 to 80, wherein the crosslinking agent is selected from the group consisting of ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylene bisacrylamide, triallyl cyanurate, and combinations thereof.

[0235] Clause 82. The hydrogel composition of any one of clauses 69 to 81, wherein the initiator is selected from the group consisting of thermal initiators, photoinitiators, and combinations thereof.

[0236] Clause 83. The hydrogel composition of clause 82, wherein the photoinitiator is selected from the group consisting of aromatic alpha-hydroxyketones, alkoxyoxybenzoins, acetophenones, monoacylphosphine oxides, bisacylphosphine oxides, and combinations thereof.

[0237] Clause 84. An ophthalmic device made from the hydrogel composition of any one of clauses 69 to 83.

[0238] Clause 85. An ophthalmic device according to Clause 84, wherein the ophthalmic device is a contact lens.

[0239] Some embodiments of the present disclosure will now be described in detail in the following examples. [Example]

[0240] Some embodiments of the present disclosure will now be described in detail in the following examples.

[0241] IOL Test Methods Unless otherwise stated, IOL test samples for refractive index, Abbe number, water content, and glass transition temperature were extracted and dried polymer buttons.

[0242] Refractive Index Test Method: Refractive index (RI) was measured using an Anton Paar Abbemat WR wavelength refractometer. Prior to use, the instrument was equilibrated at either 25°C or 35°C for a minimum of 1 hour. The measurement wavelength was set to 589.3 nanometers. Using a pair of tweezers, the sample was placed on a quartz plate. The instrument lid was closed, and a custom-made metal tube weighing 1400 grams was placed on the lid to maintain constant pressure. The refractive index was recorded after a 60-second dwell time. Measurements were performed on three polymer button samples, and the average was reported. In some examples, where noted, measurements were performed on both sides of three polymer buttons, and the average of six measurements was reported.

[0243] Abbe Number Test Method: Following the steps for measuring the refractive index at 589.3 nm, the refractive index at 486.1 nanometers and 656.3 nanometers were measured. Measurements were performed on three polymer buttons, and for each polymer button, refractive index measurements at all three wavelengths were completed before measuring the next iteration. The Abbe number was calculated as follows: Abbe number V=(n D -1) / (n F -n C ), In the formula, n D , n F , and n C are the refractive indices of the material at the wavelengths of the Fraunhofer D, F, and C spectral lines (589.3 nanometers, 486.1 nanometers, and 656.3 nanometers, respectively). The average of three measurements is reported. In some examples, where noted, measurements were taken on both sides of three polymer buttons, and the average of six measurements is reported.

[0244] Moisture Content Test Method: Moisture content (WC) was determined gravimetrically. In this method, three dry polymer discs were individually weighed and transferred to individual glass scintillation vials using sharp-tipped metal tweezers. Approximately 10 mL of HPLC-grade water was transferred to each vial, and the samples were incubated at 37°C for 14 days. After incubation, the polymer discs were removed from the vials using sharp-tipped metal tweezers, and all sides (flat surfaces and edges) were briefly blotted with lint-free blotting paper to remove surface / excess water. Using dry tweezers, each polymer disc was placed on a tared weighing pan and weighed. The moisture content of the polymer discs was calculated as follows: % moisture content = (wet weight - dry weight) / wet weight × 100. The mean and standard deviation of the moisture content were calculated, and the mean value was reported as the percent moisture content of the discs.

[0245] UV-Visible Spectroscopy Test Method: The UV-visible spectra of compounds in solution were measured using a Perkin Elmer Lambda 45 or an Agilent Cary 6000i UV / VIS scanning spectrometer. The instruments were allowed to thermally equilibrate for at least 30 minutes before use. For the Perkin Elmer instrument, the scan range was 200-800 nm, the scan speed was 960 nm per minute, the slit width was 4 nm, the mode was set to transmittance or absorbance, and baseline correction was selected. For the Cary instrument, the scan range was 200-800 nm, the scan speed was 600 nm per minute, the slit width was 2 nm, and the mode was set to transmittance or absorbance. It is important to ensure that the exterior of the cuvette is completely clean and dry and that no air bubbles are present within the cuvette. Measurement reproducibility is improved when the reference cuvette and its lens holder remain constant and all samples use the same sample cuvette and its lens holder; ensure both cuvettes are properly inserted into the instrument.

[0246] The UV-visible spectra of disks formed from the claimed compositions were measured on a Perkin Elmer Lambda 45 UV / VIS or Agilent Cary 6000i UV / VIS scanning spectrometer, as described above, using a custom-made adjustable holder to position the disk in the beam. The custom-made adjustable holder was V-shaped, allowing the disk to slide into position. Baseline correction was performed using an empty custom-made adjustable holder. To obtain UV-VIS spectra on wet disks, another custom-made adjustable holder was used to hold a quartz cuvette designed to hold the disk in place across the incident light beam. Baseline correction was performed using the custom-made adjustable holder and an empty cuvette (no solvent, no disk). All lenses were fabricated using the same mold to ensure consistent sample thickness. Absorbance or transmission spectra were obtained by averaging data from three individual disks.

[0247] Glass Transition Temperature Test Method: Due to the thickness and / or brittleness of the polymer disc, test samples were cut from the center of the polymer disc using a razor blade. Samples could not be punched out like thin films. Test samples were analyzed (in duplicate) on a DSC Q2000 TA instrument under a nitrogen gas atmosphere at a heating rate of 10°C / min and a cooling rate of 5°C / min. The glass transition temperature was determined from the second heating scan unless otherwise noted.

[0248] Dynamic Mechanical Analysis (DMA): Dynamic mechanical analysis was performed in tension mode using a TA Instruments solid analyzer, model RSA G2. Rectangular specimens measuring approximately 3 mm wide, 5 mm long, and 0.75 mm thick were cut from the polymer discs. The storage modulus (E') was determined at 22 °C in the elastic region at a strain of 1 Hz. Tan delta (E" / E') was also determined by temperature sweep analysis from 10 °C to 40 °C at a temperature sweep rate of 2 °C / min and a strain frequency of 1 Hz, where E'' is the loss modulus. E' and E" are in megapascals (MPa). Tan delta is reported as the temperature (°C) of maximum damping (tan δmax) and is used to estimate the glass transition temperature of the material.

[0249] Contact Lens Testing Methods Unless otherwise noted, the test methods used to characterize the contact lens test samples are described below. Standard deviations are shown in parentheses or as ± in the tables.

[0250] The water content (WC) was determined by weight. The lenses were equilibrated in the packing solution for 24 hours. Three test lenses were each removed from the packing solution using a sponge-tipped swab and placed on a blotting wipe that had been moistened with packing solution. Both sides of the lens were in contact with the paper. Using tweezers, the test lenses were placed in a pre-weighed weighing dish and weighed. Two additional sets of samples were prepared and weighed. All weight measurements were performed three times, and the average of these values ​​was used in the calculations. The wet weight was determined as the combined weight of the weighing dish and wet lens minus the weight of the weighing dish alone.

[0251] Dry weight was measured by placing the sample pan in a vacuum oven preheated to 60°C for 30 minutes. Vacuum was applied until a pressure of at least 1 inch Hg was reached, although lower pressures are acceptable. The vacuum valve and pump were turned off and the lenses were allowed to dry for at least 12 hours (usually overnight). The purge valve was opened to admit dry air or dry nitrogen gas. The oven was allowed to reach atmospheric pressure. The weighing pan was removed and weighed. The dry weight was determined as the total weight of the weighing pan and dry lens minus the weight of the weighing pan alone. The water content of the test lenses was calculated as follows: % water content = (wet weight - dry weight) / wet weight x 100. The mean and standard deviation of the water content were calculated and the mean was reported as the percent water content of the test lenses.

[0252] The refractive index (RI) of contact lenses was measured using a Leica ARIAS 500 Abbe refractometer in manual mode or a Reichert ARIAS 500 Abbe refractometer in automatic mode with a prism gap distance of 100 micrometers. The instrument was calibrated at 20°C (±0.2°C) using deionized water. The prism assembly was opened and the test lens was placed on the lower prism between the magnetic dots closest to the light source. If the prism was dry, a few drops of saline were applied to the bottom prism. The front curve of the lens was brought into contact with the bottom prism. The prism assembly was then closed. The controls were adjusted so that the shadow line appeared in the reticle field, and the refractive index was then measured. RI measurements were performed on five test lenses. The average RI calculated from the five measurements was recorded as the refractive index, along with its standard deviation.

[0253] Haze was measured by placing a hydrated test lens in borate-buffered saline in a clear glass cell at room temperature, placed on a flat black background, illuminating it from below at a 66-degree angle relative to the normal to the lens cell using a fiber-optic lamp (Dolan-Jenner PL-900 fiber-optic light source with a 0.5-inch diameter light guide). An image of the lens normal to this lens cell was captured from above with a video camera (DVC 1300C:19130 RGB camera with a suitable zoom camera lens) positioned 14 mm above the lens holder. Background scattering was subtracted from the lens scattering by subtracting an image (baseline) of a blank cell with borate-buffered saline using EPIX XCAP V3.8 software. High-edge scattering (ground glass) values ​​were obtained by adjusting the light intensity to a 900-910 mean grayscale. Background scattering (BS) values ​​were measured using a glass cell filled with saline. The subtracted scattered light image was integrated over the central 10 mm of the lens and then quantitatively analyzed by comparison with a ground-glass standard. The light intensity / power settings were adjusted to achieve a mean grayscale value within the range of 900–910 for the ground-glass standard; at this setting, the baseline mean grayscale value ranged from 50–70. The mean grayscale values ​​for the baseline and ground-glass standard were recorded and used to create a scale from zero to 100, respectively. For the grayscale analysis, the mean and standard deviation for the baseline, ground-glass, and each test lens were recorded. For each lens, a scale value was calculated according to the equation: The scale value is equal to the mean grayscale value (lens minus baseline) divided by the mean grayscale value (ground-glass minus baseline) multiplied by 100 to obtain a percentage. Three to five test lenses were analyzed, and the results were averaged and reported as % Haze.

[0254] Oxygen permeability (D k) was determined using the polarographic method outlined in ISO 9913-1:1996 and ISO 18369-4:2006 with the following modifications. Measurements were performed in a 2.1% oxygen environment, created by equipping the test chamber with nitrogen and air inlets set to the appropriate ratio of, for example, 1800 mL / min nitrogen and 200 mL / min air. t / Dk was calculated using the adjusted oxygen concentration. Borate-buffered saline was used. Instead of using MMA lenses, a pure humidified nitrogen environment was used to measure the dark current. The lenses were not wiped before measurement. Instead of using lenses with various thicknesses (t) measured in centimeters, four lenses were stacked. A curved sensor was used instead of a flat sensor, resulting in a radius of 7.8 mm. Calculations for a 7.8 mm radius sensor and 10% (v / v) air flow were performed as follows: D k / t=(measured current-dark current)X(2.97x10-8mL O2) / (μA-sec-cm 2 -mmHg)

[0255] Edge compensation is the D k associated with.

[0256] All D below 90 bar k For values, t / D k (Edge correction)=[1+(5.88xt)]X(t / D k )

[0257] 90-300 bar D k For values, t / D k (Edge correction)=[1+(3.56xt)]X(t / D k )

[0258] D greater than 300 bar k For values, t / D k (Edge correction)=[1+(3.16xt)]X(t / D k )

[0259] Non-edge correction D k is calculated from the inverse of the slope obtained from linear regression analysis of the data, where the x variable is the center thickness in centimeters and the y variable is t / D k On the other hand, the edge correction D k ("EC D k ") was calculated from the inverse of the slope obtained from a linear regression analysis of the data, with the x variable being the center thickness in centimeters and the y variable being the edge-corrected t / D k The obtained D k Values ​​were reported in barrers.

[0260] Lens wettability was measured using the sessile drop technique with a KRUSS DSA-100™ instrument at room temperature, using deionized water as the probe solution (sessile drop). The lenses to be tested were rinsed in deionized water to remove the packaging solution. Each test lens was placed on lint-free blotting paper moistened with the packaging solution. Both sides of the lens were contacted with the blotting paper to remove surface water without drying the lens. To ensure proper flattening, the lens was placed "dish-side down" on the convex surface of a contact lens plastic mold. The plastic mold and lens were placed in a drop fixture holder to ensure proper center syringe alignment. A 3-4 microliter drop of deionized water was formed on the tip of the syringe using DSA 100-Drop Shape Analysis software, ensuring the drop hung away from the lens. The drop was smoothly expelled onto the surface of the lens by moving the needle down. The needle was immediately withdrawn after dispensing the drop. The drop was allowed to equilibrate on the lens for 5-10 seconds, and the contact angle was measured between the drop image and the lens surface. Typically, 3-5 lenses were evaluated, and the average contact angle was reported.

[0261] The wettability of the lenses was also evaluated by measuring the dynamic contact angle. Dynamic contact angles were determined at room temperature using a Cahn DCA-315 instrument by the Wilhelmy plate method, using deionized water as the probe solution (Cahn DCA). Experiments were performed by immersing a lens specimen of known parameters in a packing solution of known surface tension, while a high-sensitivity balance measured the force exerted on the sample due to wetting. The advancing contact angle of the packing solution on the lens was determined from force data collected during sample immersion. The receding contact angle was similarly determined from force data while the sample was withdrawn from the liquid. The Wilhelmy plate method is based on the following equation: Fg = γρ cos θ - where F = wetting force between the liquid and the lens (mg), and g = gravitational acceleration (980.665 cm / sec 2 ), γ = surface tension of the probe liquid (dyne / cm), ρ = perimeter of the contact lens at the liquid / lens meniscus (cm), θ = dynamic contact angle (degrees), and B = buoyancy (mg). B is zero at zero depth of immersion. Four test strips were cut from the central region of the contact lens. Each strip was approximately 5 mm wide and equilibrated in the packing solution. Each sample was then cycled four times and the results were averaged to obtain the advancing and receding contact angles of the lens. The advancing and receding dynamic contact angles are listed in the table in that order. However, in the claims, only the advancing dynamic contact angle is used.

[0262] The mechanical properties of the contact lenses were measured using an Instron model 1122 or 5542 tensile tester equipped with a load cell and pneumatic grip controls. A minus one diopter lens was the preferred lens geometry due to its uniform thickness profile at the center. Dogbone-shaped samples cut from a -1.00 diopter lens, having a length of 0.522 inches, an "ear" width of 0.276 inches, and a "neck" width of 0.213 inches, were placed in the grips and stretched to failure at a constant strain rate of 2 inches per minute. The center thickness of the dogbone samples was measured using an electronic thickness gauge prior to testing. The initial gauge length (L) of the sample was 0.522 inches. o) and the sample length at break (L f At least five specimens of each composition were measured and the average value was used to calculate the percent elongation to break: Percent Elongation = ((L f -L o ) / L o ) x 100. The tensile modulus (M) was calculated as the slope of the initial linear portion of the stress-strain curve, and the units of modulus are pounds per square inch or psi. The tensile strength (TS) was calculated from the peak load and the original cross-sectional area. Tensile strength = peak load divided by the original cross-sectional area, and the units of tensile strength are psi. The toughness was calculated from the energy to break and the original volume of the sample. Toughness = energy to break divided by the original volume of the sample. The units of toughness are in-lbs / in 3 The elongation to break (ETB) was also recorded as a percentage of the strain at break.

[0263] Polymer molecular weights were determined by size-exclusion chromatography with multi-angle light scattering (SEC-MALS). A typical SEC-MALS setup was performed at 65°C with a flow rate of 0.6 mL / min, using a suitable solvent such as 1-propanol (or THF) with or without 10 mM LiBr (or another commonly used salt) as the mobile phase. Three Tosoh Biosciences TSK gel columns were used in series: SuperAW3000 4 μm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 60,000 g / mol), SuperAW4000 6 μm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 400,000 g / mol), and SuperAW5000 7 μm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 4,000,000 g / mol), with an online Agilent 1200 UV / VIS diode array detector, a Wyatt Optilab rEX interference refractometer, and a Wyatt mini-DAWN Treos multi-angle laser scattering (MALS) detector (λ = 658 nm). A dη / dc value of 0.074 mL / g at 30 °C (λ = 658 nm) was used for absolute molecular weight determination. Absolute molecular weight and polydispersity data were calculated using the Wyatt ASTRA 6.1.1.17 SEC / LS software package.

[0264] Common Abbreviations The following abbreviations are used throughout the examples and have the following meanings: IOL: Intraocular lens CL: Contact lenses TL03 Light: Phillips TLK 40W / 03 bulb LED: Light-emitting diode RMM: reactive monomer mixture RI(25): Refractive index measured at 25°C RI(35): Refractive index measured at 35°C Abbe number (25): Abbe number measured at 25°C Abbe number (35): Abbe number measured at 35°C T g : Glass transition temperature (°C) determined by differential scanning calorimetry (DSC) WC: water content Wt.%: weight percent UV-VIS: Ultraviolet-visible (spectroscopy) UV-HEV or UV / HEV: Ultraviolet and High-Energy Visible Light NMR: Nuclear magnetic resonance (spectroscopy) TLC: Thin Layer Chromatography h: time RT: room temperature mm: millimeters cm: centimeters μm: micrometer nm: nanometer mL: milliliter N: Normal (equivalents / liter) M: moles (moles / liter) mM: millimole (mmol / liter) μL: microliter mW: milliwatt g / mol: grams per mole M n :Number average molecular weight Da or Dalton: grams per mole kDa: kilodalton λ: Wavelength rpm: revolutions per minute psi: pounds per square inch BC: Plastic mold with curved bottom made from PP, TT, Z, or blends thereof FC: A plastic mold with a curved front made from PP, TT, Z, or a blend of these. PP: Polypropylene, a homopolymer of propylene TT: Tuftec (Asahi Kasei Chemicals), a hydrogenated styrene butadiene block copolymer Z: Zeonor (Nippon Zeon Co Ltd), a polycycloolefin thermoplastic polymer

[0265] Solvent abbreviations ACN: acetonitrile EtOAc: ethyl acetate MeOH: Methanol DCM: dichloromethane or methylene chloride Et3N: Triethylamine 3E3P: 3-ethyl-3-pentanol DO: 3,7-dimethyl-3-octanol (Vigon) DIW: Deionized water IPA: Isopropyl alcohol PG: 1,2-propylene glycol PBS Phosphate-buffered saline PS: Borate Buffer Package Solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in enough deionized water to fill a 2-liter volumetric flask. BAGE: Boric acid glycerol ester (the molar ratio of boric acid to glycerol was 1:2): 299.3 grams (mol) of glycerol and 99.8 grams (mol) of boric acid were dissolved in 1247.4 grams of 5% (wt / wt) aqueous ethylenediaminetetraacetic acid solution in a suitable reactor, then heated to 90-94°C with stirring under moderate vacuum (2-6 torr) for 4-5 hours and cooled to room temperature.

[0266] RMM component abbreviations HEMA: 2-hydroxyethyl methacrylate (Bimax) GMMA: 2,3-dihydroxypropyl methacrylate (Polysciences) DMA: N,N-dimethylacrylamide (Jarchem) MMA: methacrylic acid (Acros) PVP K90: Poly(N-vinylpyrrolidone) (ISP Ashland) SiMAA: 2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (Toray), or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate

[0267] [ka] tBu-SiMAA: 3-(3-(1,5-di-tert-butyl-1,1,3,5,5-pentamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate (Shin Etsu)

[0268] [ka] mPDMS: mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane, (M n = 800-1500 g / mol) (Gelest) HO-mPDMS: mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminated polydimethylsiloxane (M n = 400-1400 g / mol) (Ortec or DSM-Polymer Technology Group) OH-mPDMS (n=4):

[0269] [ka] OH-mPDMS (n=14) (Ortec), an oligomeric macromer with a number-average degree of polymerization (DP) of 14:

[0270] [ka] NHA: n-Hexyl acrylate [CAS 2499-95-8] (Sigma-Aldrich) NBA: n-butyl acrylate HBA: 4-hydroxybutyl acrylate [CAS 2478-10-6] (TCI or BASF) E2EA: 2-(2-ethoxyethoxy)ethyl acrylate PEA: 2-phenylethyl acrylate [CAS 3530-36-7] (MPD) PEMA: 2-Phenylethyl methacrylate [CAS 3683-12-3] PPA: 3-phenylpropyl acrylate [CAS 85909-41-7] CHA: Cyclohexyl acrylate [CAS 3066-71-5] (TCI or Alfa Aesar) CHMA: Cyclohexylmethyl acrylate

[0271] [ka] CHEA: 2-cyclohexylethyl acrylate

[0272] [ka] CHPA: 3-cyclohexylpropyl acrylate

[0273] [ka] EGDCA: Ethylene glycol dicyclopentenyl ether acrylate [CAS 65983-31-5] (Sigma-Aldrich)

[0274] [ka] BCHA: ((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)methyl acrylate or cycloacrylate or [(1S,4S)-2-bicyclo[2.2.1]hept-5-enyl]methyl prop-2-enoate [CAS 95-39-6] (Monomer-Polymer and DAJAC Labs Inc.)

[0275] [ka] CAA: Cinnamyl acrylate

[0276] [ka] TCDA: Tricyclo[5.2.1.02,6]decane dimethanol diacrylate or dimethyloltricyclodecane diacrylate [CAS 42594-17-2] (Sigma-Aldrich or Kyoeisha Chemical Co.)

[0277] [ka] mPEG 300: Poly(ethylene glycol) methyl ether methacrylate (Mn = 300 g / mol) (Sigma-Aldrich)

[0278] [ka] PEG-OH 200: Poly(ethylene glycol) methacrylate (Polysciences; molecular weight of the PEG block is 200 g / mol) PEG-OH 360: Poly(ethylene glycol) methacrylate (Mn = 360 g / mol) (Sigma-Aldrich)

[0279] [ka] PEG-OH-N2:

[0280] [ka] PEG-OH-N3:

[0281] [ka] PEG-OH-N4:

[0282] [ka] PEG-OH-N5:

[0283] [ka] PEG-OH-N6:

[0284] [ka] PEG-OH-N7:

[0285] [ka] PEG-OH-N8:

[0286] [ka] PEG-OH-MIX1:

[0287] [ka] Mixtures of oligomers PEG-OH-N4, PEG-OH-N5, PEG-OH-N6, PEG-OH-N7, and PEG-OH-N8 were formulated to exhibit a molecular mass distribution of POISCENE centered around PEG-OH-N6. PEG-OH-MIX2:

[0288] [ka] Mixtures of oligomers PEG-OH-N2, ​​PEG-OH-N3, PEG-OH-N4, PEG-OH-N5, PEG-OH-N6, PEG-OH-N7, and PEG-OH-N8 were formulated to exhibit a molecular mass distribution of POISCENE centered around PEG-OH-N5. PEPEA: Poly(ethylene glycol) phenyl ether acrylate [CAS#56641-05-5, M n = 324 g / mol] (Sigma-Aldrich)

[0289] [ka] BCEA: 2-((butylcarbamoyl)oxy)ethyl acrylate (Sigma-Aldrich)

[0290] [ka] OPEA: 2-oxo-2-(pentylamino)ethyl acrylate

[0291] [ka] MOPEA: 2-oxo-2-((3-methoxypropyl)amino)ethyl acrylate

[0292] [ka] OAOEA: 2-oxo-2-(octylamino)ethyl acrylate

[0293] [ka] DAOEA: 2-oxo-2-(decylamino)ethyl acrylate

[0294] [ka] CHOPE: 2-oxo-2-((cyclohexylmethyl)amino)ethyl acrylate

[0295] [ka] BZOEA: 2-oxo-2-(benzylamino)ethyl acrylate

[0296] [ka] OPEEA: 2-oxo-2-(phenethylamino)ethyl acrylate

[0297] [ka] OTPEA: 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl acrylate

[0298] [ka] OPAEA: 2-oxo-2-((2-pentanamidoethyl)amino)ethyl acrylate

[0299] [ka] DHOEMA: 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl methacrylate

[0300] [ka] DMAOEMA: 2-(dimethylamino)-2-oxoethyl methacrylate

[0301] [ka] EGDMA: Ethylene glycol dimethacrylate (Esstech) TMPTMA: Trimethylolpropane trimethacrylate (Esstech) TRGDMA: Triethylene glycol dimethacrylate (Sigma Aldrich) TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) Tegomer MA: Bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (M n = 2000 g / mol, n = 20) (Shin Etsu)

[0302] [ka] BHPMA-PDMS: Bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (M n = 2100 g / mol, n = 21) (Shin Etsu)

[0303] [ka] TCDA: Tricyclo[5.2.1.02,6]decane dimethanol diacrylate or dimethyloltricyclodecane diacrylate [CAS 42594-17-2] (Sigma-Aldrich or Kyoeisha Chemical Co.)

[0304] [ka] Norbloc: 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole (Janssen) Blue HEMA: 1-amino-4-[3-(4-(2-methacryloyloxy-ethoxy)-6-chlorotriazin-2-ylamino)-4-sulfophenylamino]anthraquinone-2-sulfonic acid (described in U.S. Pat. No. 5,944,853) RB247: 1,4-bis[2-methacryloxyethylamino]-9,10-anthraquinone (CAS#109561-07-1) UVB: 3-(3-(tert-butyl)-5-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenyl)-propyl methacrylate or 2-methylacrylic acid, 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester (Adesis)

[0305] [ka] HEVB: 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate

[0306] [ka] HEVC: 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate

[0307] [ka] Omnirad 403: Bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (IGM Resins) Omnirad 1173: 2-hydroxy-2-methyl-1-phenylpropanone (IGM Resins) Omnirad 1700: a mixture of 25% by weight of Omnirad 403 and 75% by weight of Omnirad 1173 (IGM Resins) Omnirad 1870: a mixture of 70% by weight of Omnirad 403 and 30% by weight of Omnirad 1173 (IGM Resins) Omnirad 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [CAS 162881-26-7] (IGM Resins) AIBN: Azobisisobutyronitrile [CAS 78-67-1] BHT: Butylated hydroxytoluene, also known as dibutylhydroxytoluene

[0308] preparation Preparation 1: The synthesis of 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (HEVB) is shown in Scheme 1.

[0309] [ka]

[0310] Methyl cyanoacetate (40 grams, 0.4037 moles) and 25 mL of dichloromethane were stirred in a three-necked 500 mL round-bottom flask equipped with a reflux condenser under a nitrogen atmosphere. After 2-aminoethanol (23.8 grams, 0.3897 moles, approximately 0.97 equivalents) was added to the solution via an addition funnel, the temperature rose and the methylene chloride began to reflux. After the exotherm subsided, external heat was applied to maintain gentle reflux for a total of 2 hours, after which no ethanolamine was observed by thin-layer chromatography.

[0311] The reaction may also be carried out at room temperature and is complete within a few hours. The mixture was cooled to room temperature, and all methylene chloride was evaporated under reduced pressure. The residual oil was washed three times with 50 mL of ethyl acetate to remove unreacted starting material and nonpolar impurities. The residual ethyl acetate was then removed under reduced pressure, and the resulting oil was used for acylation without further purification.

[0312] The crude N-2-hydroxyethylacetamide derivative was dissolved in 150 mL of dichloromethane containing 40 grams of pyridine (approximately 0.5 moles) in a three-neck round-bottom flask equipped with a reflux condenser, an addition funnel, and a magnetic stir bar. The flask was immersed in an ice bath and cooled to approximately 0°C. Methacryloyl chloride (45.76 g, approximately 0.44 moles) was added dropwise through the addition funnel, and the resulting reactive mixture was allowed to warm to room temperature while constantly stirring the system. Methanol (20 mL) was added to the flask to quench any unreacted methacryloyl chloride. Volatile components were removed by rotary evaporation under reduced pressure, and the crude product was dissolved in 800 mL of dilute aqueous HCl. The resulting aqueous solution was extracted three times with 100 mL of hexane in a separatory funnel to remove any nonpolar impurities. The organic layer was discarded. Sodium chloride was added to the aqueous layer, which was then extracted three times with 300 mL of ethyl acetate. Approximately 50 milligrams of BHT was added as an inhibitor to the combined organic fractions, and the ethyl acetate was removed by rotary evaporation under reduced pressure. The crude product crystallized from solution during solvent removal. When approximately 100 mL of ethyl acetate remained in the flask, 250 mL of hexane was added, and the crude product was isolated by vacuum filtration using a fritted glass funnel. Thin-layer chromatography indicated the presence of a single compound. The filter cake was washed twice with 150 mL of hexane and then dried under vacuum at 40°C to yield 53 grams (approximately 70% yield) of 2-(2-cyanoacetamido)ethyl methacrylate. 1 H NMR (500MHz, CDCl3) δ1.93(3H,s,CH3),3.36(2H,s,CNCH2),3.60(2H,dd,CH2NH),4.26(2H,t,CH2OC=O),5.59(1H,m,vinylic),6.11(1H,bs,vinylic),6.52(1H,bs,NH).

[0313] A mixture of 9H-thioxanthen-9-one (2.12 grams, 0.01 mole) and thionyl chloride (5 mL, 8.2 grams, approximately 0.07 mole) was refluxed in a 50 mL round-bottom flask under a nitrogen atmosphere with constant stirring. After 2 hours, the red solution was evaporated to dryness to ensure all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (2.3 grams, 0.0117 mole, approximately 1.17 equivalents) and 15 mL of dichloromethane were added, and the resulting reaction mixture was heated to reflux under a nitrogen blanket. The reaction was monitored by thin-layer chromatography. After 2 hours, no change in the chromatogram was observed, so the reactive mixture was cooled to room temperature. After passage through a short silica gel column (CH2Cl2, followed by 8 weight percent EtOAc in CH2Cl2), 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (HEVB) was isolated as yellow crystals (3.2 grams, 82% yield). 1 H NMR (500 MHz, CDCl) δ 1.84 (3H, s, CH), 3.47 (2H, m, CHNH), 4.01 (2H, t, CHOC=O), 5.55 (1H, m, vinylic), 5.91 (1H, bs, NH), 5.98 (1H, bs, vinylic), 7.24 (1H, t, Ar-H), 7.31 (1H, t, Ar-H), 7.39 (2H, m, Ar-H), 7.49 (1H, d, Ar-H), 7.55 (1H, m, Ar-H), 7.61 (1H, d, Ar-H), 8.04 (1H, m, Ar-H). The UV-VIS transmission spectrum of HEVB in 0.2 mM methanol is shown in Figure 1.

[0314] Preparation 2: Synthesis of 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate (HEVC) as shown in Scheme 2.

[0315] [ka]

[0316] Synthesis of 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl acetate: 3-Hydroxy-9H-xanthen-9-one (42.4 grams, 0.2 moles), 70.0 grams of Cs2CO3 (0.2 moles), and sodium iodide (cat. 200 milligrams) were dried under vacuum in a 500 mL round-bottom flask equipped with a magnetic stir bar. Anhydrous DMSO (250 mL) was added, followed by 2-chloroethyl methacrylate (30.0 grams, 0.2 moles). The reaction mixture was heated at 70 °C overnight. TLC monitoring indicated complete consumption of the hydroxyxanthenone, along with the formation of less polar derivatives. The reaction mixture was cooled to room temperature and slowly poured into dilute aqueous hydrochloric acid with constant stirring. After stirring for 30 minutes, the off-white solid was isolated by vacuum filtration using a fritted glass funnel. The filter cake was washed with deionized water, followed by two 200 mL washes with hexane. 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl acetate was dried in vacuo at 60° C. to constant weight.

[0317] Synthesis of 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl alcohol: 27 grams of 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl acetate was stirred in approximately 700 mL of methanol at room temperature while 20 mL of 10 N aqueous sodium hydroxide was added to the mixture, followed by approximately 30 mL of deionized water. TLC monitoring indicated that the hydrolysis reaction was complete within minutes. The mixture was slowly acidified by the addition of dilute aqueous hydrochloric acid, followed by the addition of 150 mL of deionized water while the system was constantly stirred. The 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl alcohol was isolated by vacuum filtration using a fritted glass funnel, washed with additional water, and finally dried in a vacuum oven at 60°C.

[0318] Synthesis of 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl methacrylate: 25 grams of 3-((9-oxo-9H-xanthen-3-yl)oxy)propanol and 15 mL (10.89 grams) of triethylamine were stirred in 300 mL of anhydrous acetonitrile in a 1-liter, three-necked round-bottom flask equipped with a magnetic stir bar and a reflux condenser. Methacryloyl chloride (9.9 grams) was added dropwise to the flask, and the mixture was stirred for 1 hour. The volatile components were evaporated under reduced pressure, and the resulting solid was washed, filtered through a fritted glass funnel, and rinsed with deionized water. The residue was further washed with dilute aqueous hydrochloric acid, followed by further washings with deionized water, and finally with hexane. 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl methacrylate was then dried in a rotary evaporator with the bath temperature maintained below 20°C.

[0319] Synthesis of 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate (HEVC): 6.76 grams of 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl methacrylate and 15 mL of thionyl chloride were heated at 65° C. (mantle temperature) for 2 hours in a round-bottom flask equipped with a magnetic stir bar and a reflux condenser. The mixture was cooled to room temperature, and excess thionyl chloride was evaporated under reduced pressure while maintaining the bath temperature below 20° C. 3.96 grams of malononitrile was added to the flask, followed by 25 mL of anhydrous dichloromethane, and the mixture was stirred and heated to gentle reflux for 2 hours. The mixture was cooled to room temperature and then passed through a short silica gel plug eluting with methylene chloride. The volatile components were evaporated under reduced pressure while maintaining the temperature below 20° C., after which the solid was suspended in cold methanol (100 mL) and stirred for 20 minutes. The crude product was isolated by vacuum filtration, and the filter cake was washed with additional cold methanol. 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate was further purified by passing through a silica gel column eluting with methylene chloride. 1H NMR (500 MHz, CDCl3) δ 1.95 (3H, CH3), 2.25 (2H, m, CH2), 4.20 (2H, t, CH2 benzylic), 4.37 (2H, t, CHO ester), 5.59 (1H, m, vinylic), 6.12 (1H, m, vinylic), 6.90 (1H, d, Ar-H), 6.97 (1H, dd, Ar-H), 7.40 (1H, ddd, Ar-H), 7.45 (1H, dd, Ar-H), 7.68 (1H, ddd, Ar-H), 8.50 (1H, d, Ar-H), 8.57 (1H, dd, Ar-H). The UV-VIS transmission spectrum of HEVC in 0.2 mM methanol is shown in Figure 1.

[0320] Preparation 3: Synthesis of cyclohexylmethyl acrylate (CHMA): Cyclohexylmethanol (25.0 grams, 219.0 mmol) and triethylamine (33.46 grams, 330.7 mmol) were dissolved in dichloromethane (450 mL) and cooled to approximately 0°C using an ice bath. While maintaining a constant temperature of approximately 0°C, acryloyl chloride (29.74 grams, 328.5 mmol) was added over 20 minutes. After the addition was complete, the reaction mixture was stirred at 0°C for 30 minutes, followed by stirring at ambient temperature overnight. The progress of the reaction was monitored using thin-layer chromatography. Upon completion of the reaction, triethylammonium chloride was filtered off, dissolved in deionized water (200 mL), and extracted with dichloromethane (3 x 50 mL). The combined organic layers were washed with water (2 x 50 mL), brine (25 mL), dried over anhydrous NaSO, vacuum filtered, and concentrated by rotary evaporation. The crude product was then passed through a short plug of silica gel and eluted with 10% ethyl acetate in n-hexane to give the desired product CHMA as a clear oil (98% yield). 1 H-NMR (500MHz, CDCl3):δ 6.39(1H,dd,J=1.0,17.0Hz),6.12(1H,dd,J=10.0,17.0Hz),5.81(1H,dd,J=1.5,10. 0Hz),3.97(2H,d,J=6.0Hz),1.76-1.62(6H,m),1.31-1.15(3H,m),0.95-1.01(2H,m).

[0321] Synthesis of 2-cyclohexylethyl acrylate (CHEA): 2-Cyclohexylethyl acrylate was prepared by the same general procedure except that 2-cyclohexylethanol was used instead of cyclohexylmethanol (99% yield). 1 H-NMR (500MHz, CDCl3):δ 6.38(1H,dd,J=1.1,17.2Hz),6.11(1H,dd,J=10.1,17.2Hz),5.80(1H,dd,J=1.4,10.1Hz),4.18(2H, t,J=7.0Hz),1.74-1.62(5H,m),1.58-1.54(2H,m),1.39-1.36(1H,m),1.27-1.13(3H,m),0.97-0.90 (2H,m).

[0322] Synthesis of 3-cyclohexylpropyl acrylate (CHPA): 3-Cyclohexylpropyl acrylate was prepared by the same general procedure except that 3-cyclohexylpropanol was used instead of cyclohexylmethanol (99% yield). 1 H-NMR (500MHz, CDCl3):δ 6.40(1H,dd,J=1.0,17.1Hz),6.11(1H,dd,J=10.0,17.1Hz),5.81(1H,dd,J=1.5,10. 0Hz),4.13(2H,t,J=7.1Hz),1.71-1.64(7H,m),1.25-1.20(6H,m),0.91-0.88(2H,m).

[0323] Preparation 4: Synthesis of N-(2-aminoethyl)pentanamide as shown in Scheme 3:

[0324] [ka]

[0325] 19.7 grams (0.17 mol) of methyl pentanoate and 4.8 grams (0.08 mol) of 1,2-ethylenediamine were added to a 100 mL three-neck round-bottom flask equipped with a stir bar and a reflux condenser containing a nitrogen gas inlet. The reaction mixture was heated at 80°C for 2 days. The reaction was monitored by TLC (20% (v / v) MeOH / EtOAc). The volatile components were removed under reduced pressure to give a solid. The crude product was purified by passing through a silica plug using a gradient elution [0-20% (v / v) MeOH:EtOAc]. The solvent was removed under reduced pressure to give the desired monoacylated product as a white solid. 1 H NMR(CDCl3,500MHz):δ 0.91(3H,t,J=5.0Hz,CH3(CH2)3CO),1.33(2H,sext,J=5.0Hz,CH3CH2CH2CH2CO),1.59(2H,qu,J=5.0Hz,CH3CH2CH2CH2CO),1.64(2H,br s,CH3CH2CH2CH2CO),2.17(2H,t,J=7.5Hz,RNHCH2CH2NH2),3.38(2H,d,J=5.5Hz,RNHCH2CH2NH2).

[0326] Example 1 Synthesis of N-alkyl-2-hydroxyacetamides as generally shown in Scheme 4:

[0327] [ka]

[0328] Methyl glycolate (0.35 mol), 120 mL of ethyl acetate, and a primary or secondary amine (0.37 mol) were added sequentially to a 500 mL round-bottom flask equipped with a stir bar, a reflux condenser with a nitrogen gas inlet, and a 5% (v / v) MeOH / EtOAc inlet. The reaction mixture was stirred at room temperature (primary amines) or elevated temperature (secondary amines) while being monitored by TLC (5% (v / v) MeOH / EtOAc). Upon completion, the volatile components were removed under reduced pressure to give an oil. 1 M hydrochloric acid was added to the oil, and the mixture was extracted three times with ethyl acetate. The organics were collected, and the volatiles were removed under reduced pressure to give an oil. For hydrophilic variations, higher yields were obtained when the aqueous workup was avoided and chromatography was performed directly on silica (0–20% (v / v) MeOH / EtOAc). This general procedure was carried out using N-pentylamine, N-cyclohexylmethylamine, N-benzylamine, N-(2-phenylethyl)amine, thiophen-2-ylmethanamine, 3-methoxypropan-1-amine, N-(2-aminoethyl)pentanamide (predicted), N-octylamine, N-decylamine, (2,2-dimethyl-1,3-dioxolan-4-yl)methanamine, and dimethylamine to produce the corresponding N-alkyl-2-hydroxyacetamides. The measured or predicted NMR spectra of the resulting N-alkyl-2-hydroxyacetamides are listed below.

[0329] Example 1A: N-pentyl-2-hydroxyacetamide: 1 H NMR(CDCl3,500MHz):δ 0.89(3H,t,J=7.3Hz,CH3CH2R),1.27-1.35(4H,m,CH3(CH2)2CH2R),1.53(2H,quint,J=6.1Hz,RCH2CH2NHR),3.27-3.31(2H,m,RCH2NHR),4.07(2H,br s,RCH2OH),6.60(1H,br s,RCH2NHR).

[0330] Example 1B: N-(cyclohexylmethyl)-2-hydroxyacetamide: 1H NMR(CDCl3,500MHz):δ 0.83-0.91(2H,m,Cy),1.04-1.21(3H,m,Cy),1.36-1.45(1H,m,Cy),1.59-1.62(1H,m,Cy), 1.64-1.67(4H,m,Cy),3.04(2H,dd,J=6.6Hz,CyCH2NHR),3.96(2H,s,RCH2OH),7.03(1H,br s,CyCH2NHR).

[0331] Example 1C: N-ベンジル-2-ヒドロキシアセトアミド: 1 H NMR(CDCl3,500MHz): δ 3.28(1H,br s,RCH2OH),4.11(2H,s,PhCH2NHR),4.46(2H,d,J=6.1Hz,RCH2OH),6.29(1H,br s,PhCH2NHR),7.26-7.29(3H,m,o,p-Ph),7.31-7.35(2H,m,m-Ph).

[0332] Example 1D: N-フェネチル-2-ヒドロキシアセトアミド: 1 H NMR(CDCl3,500MHz): δ 2.83(2H,dd,J=6.9Hz,PhCH2CH2N),3.55(2H,dd,J=6.9Hz,PhCH2CH2N),4.02(2H,s,RCH2OH),6.67(1H,br s,CH2CH2NHR),7.19(2H,d,J=7.9Hz,o-Ph),7.21-7.24(1H,m,p-Ph),7.28-7.32(2H,m,m-Ph).

[0333] Example 1E: N-(チオフェン-2-イルメチル)-2-ヒドロキシアセトアミド: 1 H NMR (CDCl3,500MHz): δ 3.53(1H,br s,RCH2OH),4.08(2H,s,RCH2OH),4.62(2H,d,J=5.9Hz,ArCH2NHR),6.94(1H,dd,J=3.4,5.1Hz,C-4),6.96-6.97(1H,m,C-5),7.04(1H,br s,ArCH2NHR),7.21(1H,dd,J=3.9,5.1Hz,C-6).

[0334] Example 1F: 2-Hydroxy-N-(3-methoxypropyl)acetamide: 1 H NMR(CDCl3,500MHz):δ 1.80(2H,dt,J=5.5,6.5Hz,OCH2CH2CH2N),3.34(3H,s,CH3OCH2),3.42(2H,t,J=6.5H z,OCH2CH2CH2N),3.48(2H,t,J=5.5Hz,OCH2CH2CH2N),4.07(2H,d,J=6.Hz,RCH2OH).

[0335] Example 1G: N-(2-(2-hydroxyacetamido)ethyl)pentanamide: 1 H NMR(CDCl3,500MHz):δ 0.93(3H,t,CH3(CH2)3CO),1.38(2H,sext,CH3CH2CH2CH2CO),1.53(2H,qu,CH3CH2CH2CH2CO),2.13 (2H,t,CH3CH2CH2CH2CO),3.66(4H,s,HN(CH2)2NH),4.42(2H,s,RCH2OH) [prediction by ChemDraw software].

[0336] Example 1H: 2-Hydroxy-N-octylacetamide: 1 H NMR(CDCl3,500MHz):δ 0.83(3H,t,J=6.5Hz,CH3CH2R),1.22-1.28(10H,m,CH3(CH2)5CH2R),1.47(2H,br qu,CH3(CH2)5CH2R),3.21(2H,dd,J=6.5,7.5Hz,RCH2NHR),3.97(2H,s,RCH2OH),4.96(1H,br s,RCH2OH),6.94(1H,br s,RCH2NHR).

[0337] Example 1I: 2-Hydroxy-N-decylacetamide: 1H NMR(CDCl3,500MHz):δ 0.87(3H,t,J=7.5Hz,CH3CH2R),1.25-1.29(14H,m,CH3(CH2)7CH2R),1.50(2H,br qu,CH3(CH2)7CH2R),3.26(2H,dd,J=5,10Hz,RCH2NHR),3.64(1H,br s,RCH2OH),4.05(2H,s,RCH2OH),6.65(1H,br s,RCH2NHR).

[0338] Example 1J: N-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-2-hydroxyacetamide: 1 H NMR(CDCl3,500MHz):δ 1.34(3H,s,OC(CH3)2O),1.43(3H,s,OC(CH3)2O),3.35-3.40(1H,m),3.55-3.59(1 H,m),3.62-3.66(1H,m),4.03-4.06(1H,m),4.11-4.13(2H,m),4.24-4.28(1H,m).

[0339] Example 1K: 2-Hydroxy-N,N-dimethylacetamide: 1 H NMR (d6-DMSO, 500 MHz): δ 2.98 (6H, s, N-CH3), 4.42 (2H, s, CH2), 4.91 (1H, s, OH) [predicted by ChemDraw software].

[0340] Example 2 Synthesis of 2-oxo-2-(alkylamino)ethyl acrylates or 2-oxo-2-(arylamino)ethyl acrylates starting from N-alkyl-2-hydroxyacetamides (R''=hydrogen or methyl) as generally shown in Scheme 5:

[0341] [ka]

[0342] N-Alkyl-2-hydroxyacetamide or N-Alkyl(R')-N-Alkyl(R'')-2-hydroxyacetamide (0.30 mol), 250 mL of dichloromethane, and triethylamine (0.36 mol) were sequentially added to a heat-gun-dried, 1-liter, three-necked, round-bottom flask equipped with a magnetic stir bar, an addition funnel, and a reflux condenser with a nitrogen gas inlet. (Meth)acryloyl chloride (0.36 mol, R''' = H or methyl) was placed in the addition funnel and slowly added to the stirred reaction mixture at room temperature over approximately 1 hour. The progress of the reaction was monitored by TLC (5% (v / v) MeOH / EtOAc). After completion, approximately 20 mL of MeOH was placed in the addition funnel and slowly added to quench the excess acid chloride. The reaction mixture was stirred at room temperature overnight (approximately 12 hours). The volatile components were then removed under reduced pressure to afford an oil. The oil was further purified by passing it through a short plug of silica gel and eluting with 20% (v / v) EtOAc / hexane. This general procedure was carried out using N-pentyl-2-hydroxyacetamide, N-(cyclohexylmethyl)-2-hydroxyacetamide, N-benzyl-2-hydroxyacetamide, N-phenethyl-2-hydroxyacetamide, and N-(thiophen-2-ylmethyl)-2-hydroxyacetamide, 2-hydroxy-N-(3-methoxypropyl)acetamide, N-(2-(2-hydroxyacetamido)ethyl)pentanamide (predicted), 2-hydroxy-N-octylacetamide, 2-hydroxy-N-decylacetamide, and 2-hydroxy-N,N-dimethylacetamide to produce the corresponding amide acrylates. The measured and predicted NMR spectra of the resulting amide acrylates are listed below.

[0343] Example 2A: 2-oxo-2-(pentylamino)ethyl acrylate (OPEA): 1H NMR(CDCl3,500MHz):δ 0.89(3H,t,J=6.8Hz,CH3CH2R),1.26-1.37(4H,m,CH3(CH2)2CH2R),1.53(2H,quint,J=7.8Hz,RCH2CH2NHR) ,3.30(2H,dd,J=7.8Hz,RCH2NHR),4.64(2H,s,RCH2OH),5.95(1H,dd,J=1.0,10.4Hz,vinylic),6.10(1H,br s,PhCH2NHR),6.20(1H,dd,J=10.4,17.2Hz,vinylic),6.51(1H,dd,J=1.0,17.2Hz,vinylic).

[0344] Example 2B: 2-((シクロヘキシルメチル)アミノ)-2-オキソエチルアクリレート (CHOPE): 1 H NMR (CDCl3, 500MHz): δ 0.89-0.95(2H,m,Cy),1.10-1.25(3H,m,Cy),1.48(1H,br s,Cy),1.64-1.74(5H,m,Cy),3.15(2H,dd,J=5.8Hz,CyCH2NHR),4.65(2H,s,RCH2OH),5.96(1H,dd,J=1.3,11.6Hz,vinylic),6.15(1H,br s,PhCH2NHR),6.21(1H,dd,J=10.4,17.2Hz,vinylic),6.51(1H,dd,J=1.3,17.2Hz,vinylic).

[0345] Example 2C: 2-(ベンジルアミノ)-2-オキソエチルアクリレート (BZOEA): 1 H NMR(CDCl3,500MHz):δ 4.46(2H,d,J=5.7Hz,PhCH2N(CH3)R),4.65(2H,s,RCH2OH),5.09(1H,dd,J=1.1,10.3Hz,vinyli c),6.16(1H,dd,J=10.3,17.6Hz,vinylic),6.47(1H,dd,J=1.1,17.6Hz,vinylic),6.71(1H,br s,PhCH2NHR),7.24-7.28(3H,m,o,p-Ph),7.31-7.34(2H,m,m-Ph).

[0346] Example 2D: 2-oxo-2-(phenethylamino)ethyl acrylate (OPEEA): 1 H NMR(CDCl3,500MHz):δ 2.84(2H,dd,J=7.0Hz,PhCH2CH2N),3.58(2H,dd,J=6.4Hz,PhCH2CH2N),4.62(2H,s,R CH2OH),5.91(1H,dd,J=1.0,10.4Hz,vinylic),6.11(1H,dd,J=10.5,17.8Hz,vinylic and 1H,br s,PhCH2NHR),6.41(1H,dd,J=1.0,17.8Hz,vinylic),7.17-7.19(1H,m,o-Ph),7.22-7.25(1H,m,p-Ph),7.29-7.32(2H,m,m-Ph).

[0347] Example 2E: 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl acrylate (OTPEA): 1 H NMR(CDCl3,500MHz):δ 4.61(2H,d,J=6.2Hz,ArCH2NHR),4.62(2H,s,RCH2OH),5.89(1H,dd,J=1.0,10.4Hz,vinylic) ,6.15(1H,dd,J=10.6,17.4Hz,vinylic),6.45(1H,dd,J=1.0,17.4Hz,vinylic),6.78(1H,br s,ArCH2NHR),6.92(1H,dd,J=3.4,5.2Hz,C-8),6.94-6.95(1H,m,C-7),7.19(1H,dd,J=1.5,5.4Hz,C-9).

[0348] Example 2F: 2-((3-methoxypropyl)amino)-2-oxoethyl acrylate (MOPEA): 11H NMR (CDCl3, 500 MHz): δ 1.77 (2H, br qu, OCH2CH2CH2N), 3.32 (3H, br s, CH3OCH2), 3.41 - 3.45 (2H, m, OCH2CH2CH2N), 3.49 - 3.52 (2H, m, OCH2CH2CH2N), 4.64 (2H, d, J = 3.5 Hz, RCH2OH), 5.94 (1H, br dd, vinylic), 6.16 (1H, br dd, vinylic), 6.49 (1H, br dd, vinylic), 6.88 (1H, br s, CH2NHR).

[0349] Example 2G: 2 - Oxo - 2 - ((2 - pentanamidoethyl)amino)ethyl acrylate (OPAEA): 1 1H NMR (CDCl3, 500 MHz): δ 0.93 (3H, t, CH3(CH2)3CO), 1.38 (2H, sext, CH3CH2CH2CH2CO), 1.53 (2H, qu, CH3CH2CH2CH2CO), 2.13 (2H, t, CH3CH2CH2CH2CO), 3.66 (4H, s, NHCH2CH2NH), 4.96 (2H, s, RCH2OH), 5.83 (1H, dd, vinylic), 6.12 (1H, dd, vinylic), 6.41 (1H, dd, vinylic) [predicted by ChemDraw software].

[0350] Example 2H: 2 - (Octylamino) - 2 - oxoethyl acrylate (OAOEA): 1 1H NMR (CDCl3, 500 MHz): δ 0.87 (3H, t, J = 3.5 Hz, CH3CH2R), 1.25 - 1.29 (10 H, m, CH3(CH2)5CH2R), 1.49 (2H, br qu, CH3(CH2)5CH2R), 3.29 (2H, dd, J = 6.5, 7.5 Hz, RCH2NHR), 4.65 (2H, s, RCH2OH), 5.95 (1H, dd, vinylic), 6.07 (1H, br s, RCH2NHR), 6.183 (1H, dd, vinylic), 6.49 (1H, dd, vinylic).

[0351] Example 2I: 2-(Decylamino)-2-oxoethyl acrylate (DAOEA): 1 H NMR(CDCl3,500MHz):δ 0.84(3H,t,J=3.5Hz,CH3CH2R),1.22-1.26(14 H,m,CH3(CH2)7CH2R),1.49(2H,br qu,CH3(CH2)7CH2R),3.26(2H,dd,J=5.0,9.0Hz,RCH2NHR),4.61(2H,s,RCH2OH),5.91(1H,dd,J=1.0,10.0Hz,vinylic),6.15-6.21(1H,br s,RCH2NHR and 1H,dd,J=7.0,10.0Hz,vinylic),6.46(1H,dd,J=1.0,7.0Hz,vinylic).

[0352] Example 2J: 2-(((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)amino)-2-oxoethyl methacrylate (DOOEMA): 1 H NMR(CDCl3,500MHz):δ 1.21(6H,s,OC(CH3)2O),2.01(3H,s,methyl),3.25-3.50(2H,m,NCH2CHOCH2O),3.62-3.87(2H,m,NCH2CHOCH2O),4.54 (1H,m,NCH2CHOCH2O),4.96(2H,s,OCH2C(O)N),6.40(1H,d,vinylic),6.48(1H,d,vinylic) [Prediction by ChemDraw software].

[0353] Example 2K: 2-(dimethylamino)-2-oxoethyl methacrylate (DMAOEMA): 1 H NMR (CDCl3,500MHz): δ 1.99(3H,s,CH2=CCH3),2.97(3H,s,NCH3),2.99(3H,s,NCH3),4.79(2H,s,OCH2C(O)N),5.64(1H,s,vinylic),6.22(1H,s,vinylic).

[0354] Example 2L: Synthesis of 2-((2,3-dihydroxypropyl)amino-2-oxoethyl methacrylate (DHOEMA) (Prophetic) as shown in Scheme 6:

[0355] [ka]

[0356] 2-(((2,2-Dimethyl-1,3-dioxolan-4-yl)methyl)amino)-2-oxoethyl methacrylate and tosylic acid are added to a methanol-dioxane solution in a 100 mL three-necked round-bottom flask equipped with a stir bar and a reflux condenser containing a nitrogen gas inlet. The reaction is monitored by TLC. Volatile components are removed under reduced pressure. The crude product is redissolved in an appropriate solvent and passed through a silica plug. Purified fractions are collected and the volatile components are removed by rotary evaporation, thereby affording the desired compound. 1 H NMR(CDCl3,500MHz):δ 2.01(3H,s,methyl),3.25-3.52(2H,m,NCH2CHOCH2O),3.62-3.87(2H,m,NCH2CHOCH2O),4.22(1H,m,NCH2 CHOCH2O),4.96(2H,s,OCH2C(O)N),6.40(1H,d,vinylic),6.48(1H,d,vinylic) [prediction by ChemDraw software].

[0357] Standard Cure, Demold, and Extraction Procedure ("SCDEP") Unless otherwise noted, all polymer discs were fabricated by the following standardized curing, demolding, and extraction procedure: Under yellow lighting, the reactive monomer mixture (RMM) was degassed under vacuum for at least 7 minutes, the container headspace was backfilled with nitrogen gas, and then immediately transferred to a filling box containing less than 0.1% to less than 0.5% (v / v) oxygen gas and with an internal temperature of ambient. Polymer discs (approximately 0.75 mm thick and 12-14 mm in diameter) were fabricated using a circular plastic mold made of polypropylene. Approximately 250 microliters of RMM was dispensed into the mold assembly, and the assembly was transferred to a curing box maintained at a temperature of 43 °C to 47 °C. They were then cured from the top and bottom for a total of 90 minutes using 435 nm LED light on both sides with the following intensity profile: 5 mW / cm. 2 for 20 minutes (2.5 mW / cm 2 Top and 2.5mW / cm 2 bottom), 10mW / cm 2 for 20 minutes (5 mW / cm 2 Top and 5mW / cm 2 bottom), 20mW / cm 2 for 20 minutes (10 mW / cm 2 Top and 10mW / cm 2 bottom), and 30 mW / cm 2 for 30 minutes (15 mW / cm 2 Top and 15mW / cm 2 (Bottom). The cured assembly was manually removed from the mold. All polymer discs were transparent and exhibited low levels of surface tack. Each disc was extracted with 2-propanol and subsequently dried using the following steps: (a) one disc was transferred to a glass jar containing 20 mL of 2-propanol and shaken at 115 rpm at 50 °C for 24 hours in an incubator / shaker; (b) the 2-propanol was completely decanted and replaced with a fresh 20 mL aliquot of 2-propanol and shaken at 115 rpm at 50 °C for 1.5 hours; (c) step (b) was repeated two more times; (d) after the final solvent decantation, the polymer discs were allowed to air dry at room temperature overnight; and (e) the discs were placed in a vacuum oven at 60–65 °C (less than 1 inch of mercury) for 7 days.

[0358] Alternative Acetonitrile Extraction Procedure ("AAEP") In some cases, polymer discs were placed in circular PEEK extraction vehicles and extracted with acetonitrile instead of 2-propanol. Each vehicle was approximately 635 mm in diameter and 8 mm thick, consisting of five circular, concave extraction chambers, each approximately 20 mm in diameter and 5 mm deep. The vehicles were designed for optimal solvent flow-through / exchange and were stackable. Stacking was achieved via a circular hole in the center of the vehicle, approximately 10 mm in diameter, and a threaded PEEK rod of appropriate diameter and length. Polymer discs were individually placed in the extraction chambers of the extraction vehicles. The vehicles were stacked, and a blank extraction vehicle (without polymer discs) was used to cap the top of the stack. The stack was placed in a glass jar, and acetonitrile was added to achieve a volume ratio of 1:14 mL of polymer discs to acetonitrile. The jar was placed on an orbital shaker at ambient conditions and shaken at 115 rpm overnight (15-17 hours). The acetonitrile was completely decanted, and a new aliquot of acetonitrile was added to achieve a volume ratio of 1:14 mL of polymer disks to acetonitrile. The glass jar was shaken at 115 rpm for 4 hours, after which a final acetonitrile exchange was performed for an additional 4 hours of extraction at 115 rpm. The stack was then removed from the glass jar, drained thoroughly, and air-dried at ambient conditions for 24 hours. For the final drying step, the stack was placed in a vacuum oven at 60°C to 65°C (less than 1 inch of mercury) for 4 days.

[0359] Examples 3 to 6 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 1. For each example, the refractive index, Abbe number, and water content were determined on the dried discs. The average refractive index, Abbe number, and water content are also listed in Table 1. The standard deviations are reported in parentheses.

[0360] [Table 1]

[0361] Examples 3-6 exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 3-6 also exhibited low water content, which can provide dimensional stability to implantable ophthalmic devices.

[0362] Examples 7 to 11 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 2. For each example, the refractive index, Abbe number, and water content were determined on the dried discs. The average refractive index, Abbe number, and water content are also listed in Table 2. The standard deviations are reported in parentheses.

[0363] [Table 2]

[0364] In Examples 7 and 8, by replacing HEVB with a lower concentration of HEVC, the refractive index remained at approximately 1.52, but the Abbe number increased from 49.85 to 53.62. Similarly, in Examples 9-11, by replacing HEVB with a lower concentration of HEVC, the refractive index remained at approximately 1.52, but the Abbe number increased from 49.8 to over 51.0. As a result, lenses with low concentrations of HEVC exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 7 and 9 also exhibited low water content, which can provide dimensional stability for implantable ophthalmic devices. The UV-VIS transmission spectra of the disks of Examples 8, 10, and 11 are shown in Figure 2. These samples absorbed essentially all light having wavelengths between 300 nanometers and 430 nanometers.

[0365] Examples 12 to 19 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Tables 3A and 3B. For each example, the refractive index, Abbe number, and water content were determined on the dried discs. The average refractive index, Abbe number, and water content are shown in Tables 3A and 3B. The standard deviations are reported in parentheses.

[0366] [Table 3]

[0367] [Table 4]

[0368] In Examples 12 and 13, by replacing HEVB with a lower concentration of HEVC, the refractive index remained at approximately 1.51, but the Abbe number increased from 49.55 to 51.64. Similarly, in Examples 14-19, by replacing HEVB with a lower concentration of HEVC, the refractive index remained at approximately 1.52, but the Abbe number increased from 49.17 to 51.93 or greater. As a result, the disks with a lower concentration of HEVC exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 12-19 also exhibited low water content, which can provide dimensional stability for implantable ophthalmic devices. The UV-VIS transmission spectra of the disks of Example 12 and Example 13 are shown in Figure 3. Example 12 absorbed essentially all light having a wavelength between 200 nanometers and 420 nanometers, while the lens of Example 13 absorbed essentially all light having a wavelength between 200 nanometers and 430 nanometers. The glass transition temperature, tan delta, and storage modulus are also shown in Tables 3A and 3B.

[0369] Examples 20 to 25 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 4. For each example, the refractive index, Abbe number, and water content were determined on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are shown in Table 4. The standard deviations are reported in parentheses.

[0370] [Table 5]

[0371] Examples 20 and 21, prepared from reactive monomer mixtures containing at least 70 weight percent EGDCA, exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials most suitable for ophthalmic devices such as intraocular lenses. When the reactive monomer mixture contained less than 70 weight percent EGDCA, only Examples 23 and 25, which contained low concentrations of HEVC, exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials most suitable for ophthalmic devices such as intraocular lenses. Examples 20-25 also exhibited low water content, which can provide dimensional stability for implantable ophthalmic devices.

[0372] Examples 26 to 32 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 5. For each example, the refractive index, Abbe number, and water content were determined on the dried discs. The average refractive index, Abbe number, and water content are shown in Table 5. The standard deviations are reported in parentheses.

[0373] [Table 6]

[0374] Examples 30 and 32, prepared from reactive monomer mixtures containing at least 70 weight percent EGDCA and HEVC, exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials most suitable for ophthalmic devices such as intraocular lenses. When the reactive monomer mixture contained less than 70 weight percent EGDCA and HEVC, as used in Examples 26-29 and 31, the samples exhibited a high refractive index of about 1.52, but an Abbe number slightly below 50, still suitable for ophthalmic devices such as intraocular lenses. Examples 26-32 also exhibited low water content, which can provide dimensional stability for implantable ophthalmic devices.

[0375] Examples 33 to 38 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 6. For each example, the refractive index, Abbe number, and water content were determined on the dried discs. The average refractive index, Abbe number, and water content are shown in Table 6. The standard deviations are reported in parentheses.

[0376] [Table 7]

[0377] Examples 33-38 exhibited both a high refractive index (greater than 1.50) and a high Abbe number (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 33-38 also exhibited low water content, which can provide dimensional stability to implantable ophthalmic devices.

[0378] Examples 39 to 67 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Tables 7-10. For each example, the refractive index, Abbe number, water content, tan delta, and storage modulus were measured on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are also listed in Tables 7-10. Standard deviations are listed in parentheses.

[0379] [Table 8]

[0380] [Table 9]

[0381] [Table 10]

[0382] [Table 11]

[0383] Examples 39-67 exhibited both a high refractive index (greater than 1.51) and a high Abbe number (greater than 51.50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 39-67 also exhibited a low water content (1-2 weight percent) that may provide dimensional stability for implantable ophthalmic devices.

[0384] Examples 68 to 73 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 11. For each example, the refractive index, Abbe number, water content, tan delta, and storage modulus were measured on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are also listed in Table 11. The standard deviations are listed in parentheses.

[0385] [Table 12]

[0386] Examples 68-73 exhibited high refractive indices (greater than 1.51) and Abbe numbers of 47.5-49.5, making these materials suitable for ophthalmic devices such as intraocular lenses. Examples 68-73 also exhibited low water content (approximately 1 weight percent) that may provide dimensional stability to implantable ophthalmic devices.

[0387] Examples 74 to 82 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Tables 12 and 13. For each example, the refractive index, Abbe number, water content, tan delta, and storage modulus were measured on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are also listed in Tables 12 and 13. The standard deviations are listed in parentheses.

[0388] [Table 13]

[0389] [Table 14]

[0390] Examples 74-80, containing 69-75 weight percent EGDCA and 0.3 weight percent HEVC, exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 52), making these materials most suitable for ophthalmic devices such as intraocular lenses. Examples 81 and 82, containing about 73 weight percent EGDCA and 2.25 weight percent HEVB, exhibited high refractive indices (greater than 1.52), but the Abbe number was reduced to about 48, making these materials most suitable for ophthalmic devices such as intraocular lenses.

[0391] Examples 74-82 also demonstrated low water content (about 0.9-2.5 weight percent) that can provide dimensional stability to implantable ophthalmic devices.

[0392] Examples 83 to 87 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 14. For each example, the refractive index, Abbe number, water content, tan delta, and storage modulus were measured on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are also listed in Table 14. The standard deviations are listed in parentheses.

[0393] [Table 15]

[0394] Examples 83-87 exhibited high refractive indices (greater than 1.52) and Abbe numbers (greater than 51), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 83-87 also exhibited low water content (about 1-1.5 weight percent) that may provide dimensional stability to implantable ophthalmic devices.

[0395] Examples 87 to 91 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Table 15. For each example, the refractive index, Abbe number, water content, tan delta, and storage modulus were measured on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are also listed in Table 15. The standard deviations are listed in parentheses.

[0396] [Table 16]

[0397] Examples 88-92 exhibited high refractive indices (greater than 1.52) and Abbe numbers (greater than 52), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 88-92 also exhibited low water content (about 1-1.5 weight percent), which may provide dimensional stability for implantable ophthalmic devices.

[0398] Examples 93 to 102 Polymer discs were fabricated using the standard cure, demold, and extraction procedure (SCDEP) using the RMMs listed in Tables 16 and 17. For each example, the refractive index, Abbe number, water content, tan delta, and storage modulus were measured on the dried discs. The average refractive index, Abbe number, water content, tan delta, and storage modulus are also listed in Tables 16 and 17. The standard deviations are listed in parentheses.

[0399] [Table 17]

[0400] [Table 18]

[0401] Examples 93-102 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 52), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 93-102 also exhibited low water content (about 1-2.5 weight percent) that may provide dimensional stability to implantable ophthalmic devices.

[0402] Removal of inhibitors from ethylene glycol dicyclopentenyl ether acrylate (EGDCA) In Examples 104-151, the inhibitor monomethyl ether hydroquinone (MEHQ) was removed from monomeric EGDCA prior to use by preparative column chromatography using activated basic alumina (Brockman Grade 1, 58 nanometers, Millipore Sigma #199443-5). The activated basic alumina was first dried at 200°C or 70°C under 50 mbar for 22 hours and then transferred to a 25 x 600 millimeter Kontes Chromaflex column (30 grams of dry alumina per 100 mL of EGDCA) equipped with a screw cap and air pressure connection in a fume hood. The alumina was covered with 1-2 centimeters of sand, and then EGDCA was added to the column, which was then capped. Air pressure was applied to produce a filtration rate of 2-3 drops per second (approximately 7 psi). The deinhibited EGDCA was collected in an amber bottle and either used immediately or stored in the refrigerator.

[0403] Examples 103 to 108 Polymer discs were prepared using the RMMs listed in Table 18 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted and dried discs (labeled "Dry" in Table 18). The average refractive index, Abbe number, tan delta, and storage modulus are shown in Table 18. Standard deviations are listed in parentheses. Some discs were then hydrated in deionized water at ambient temperature for 24 hours, after which the physical and mechanical properties were measured to determine the effect of water content and storage conditions (labeled "Hydrated" in Table 18).

[0404] [Table 19]

[0405] Examples 103-108 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 52), making these materials ideal for ophthalmic devices such as intraocular lenses. The hydrated materials of Examples 103-108 exhibited lower tan δmax and E' compared to the corresponding dry materials, suggesting that these physical properties depend on water content and, therefore, on post-lens manufacturing conditions, such as drying conditions and relative humidity. Equilibration in deionized water prior to sterilization can minimize or eliminate the dependence on water content.

[0406] Examples 109 to 113 Polymer discs were prepared using the RMM listed in Table 19 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted, dried disc (labeled "Dry" in Table 19, corresponding to 0 percent humidity). The average refractive index, Abbe number, tan delta, and storage modulus are shown in Table 19. Standard deviations are listed in parentheses. Some discs were then stored at ambient temperature under controlled relative humidity (25% or 45% relative humidity) for 24 hours, after which the physical and mechanical properties were measured to determine the effect of relative humidity on the physical properties (labeled "RH25 or RH45" in Table 19).

[0407] [Table 20]

[0408] Examples 109-113 exhibited high refractive indices (greater than 1.52) and Abbe numbers (greater than 52), making these materials ideal for ophthalmic devices such as intraocular lenses. For Examples 109-113, samples equilibrated at 25% or 45% relative humidity exhibited lower tan δmax and E' compared to the corresponding dry materials, suggesting that these physical properties depend on water content and, therefore, on post-lens manufacturing conditions, such as drying conditions and relative humidity. Equilibration in deionized water prior to sterilization can minimize or eliminate the dependence on water content.

[0409] Examples 114 to 119 Polymer discs were prepared using the RMM listed in Table 20 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted, dried disc (labeled "Dry" in Table 20, corresponding to 0 percent humidity). The average refractive index, Abbe number, water content, tan delta, and storage modulus are shown in Table 20. Standard deviations are listed in parentheses. Some discs were then stored at ambient temperature under controlled relative humidity (25% or 45% relative humidity) for 24 hours, after which the physical and mechanical properties were measured to determine the effect of relative humidity on the physical properties (labeled "RH25 or RH45" in Table 20). Some discs were then hydrated in deionized water at 37°C for 24 hours, after which the physical and mechanical properties were measured to determine the effect of water content and storage conditions (labeled "Hydration" in Table 20).

[0410] [Table 21]

[0411] Examples 114-119 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 51), making these materials ideal for ophthalmic devices such as intraocular lenses. For Examples 115-116, samples equilibrated at 25% or 45% relative humidity exhibited lower tan δmax and E' compared to the corresponding dry materials, suggesting that these physical properties depend on water content and, therefore, on post-lens manufacturing conditions, such as drying conditions and relative humidity. Equilibration in deionized water prior to sterilization can minimize or eliminate the dependence on water content.

[0412] Examples 120 to 130 Polymer discs were prepared using the RMMs listed in Tables 21 and 22 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted, dried discs (labeled "Dry" in Tables 21 and 22). The average refractive index, Abbe number, tan delta, and storage modulus are listed in Tables 21 and 22. Standard deviations are listed in parentheses. Some discs were then hydrated in deionized water at 37°C for two weeks, after which physical and mechanical properties were measured to determine the effect of water content and storage conditions (labeled "Hydrated" in Tables 21 and 22).

[0413] [Table 22]

[0414] [Table 23]

[0415] Examples 120-130 exhibited high refractive indices (greater than 1.50) and Abbe numbers (greater than 51), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 122-130, with 50-58 weight percent EGDCA, exhibited tan δmax (dry) values ​​between 22°C and 28°C and storage moduli (dry) between 15 MPa and 90 MPa, which are desirable ranges for intraocular lenses. The UV-VIS transmission spectra of the disks of Examples 126-130 are shown in Figure 4. These spectra were virtually identical, differing by less than 1% at any wavelength. These samples absorbed essentially all light with wavelengths between 300 nanometers and 430 nanometers, then transitioned between 430 nanometers and 500 nanometers, resulting in a 90% level of transmittance at longer wavelengths.

[0416] Examples 131-135 (Prophecy) Polymer discs are prepared by thermally curing the RMMs listed in Table 23 at 60-80°C for 2-24 hours and then demolded using the standard demolding procedure (SCDEP). The amount of AIBN is varied to control polymerization rate and reaction time. The polymer discs are extracted with acetonitrile (AAEP). The extracted discs are vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus are determined for the extracted, dried discs. Some discs are then hydrated in deionized water at 37°C for 2 weeks, after which the physical and mechanical properties are measured to determine the effects of water content and storage conditions.

[0417] [Table 24]

[0418] Examples 136 to 140 Polymer discs were prepared using the RMMs listed in Table 24 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined on the extracted, dried discs (labeled "Dry" in Table 24, corresponding to 0 percent humidity). The average refractive index, Abbe number, tan delta, and storage modulus are shown in Table 24. Standard deviations are listed in parentheses. Some discs were then hydrated in deionized water at 37°C for two weeks, after which the physical and mechanical properties were measured (labeled "Hydrated" in Table 24). Other discs were then stored at ambient temperature under controlled relative humidity (25% or 45% relative humidity) for 24 hours, after which the physical and mechanical properties were measured to determine the effect of relative humidity on the physical properties (labeled "RH25 or RH45" in Table 24).

[0419] [Table 25]

[0420] Examples 136-140 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. For Example 137, samples equilibrated at 25% or 45% relative humidity exhibited lower tan δ compared to the corresponding dry materials. max and E', suggesting that these physical properties depend on water content and therefore on post-manufacturing conditions of the lenses, such as drying conditions and relative humidity. Equilibration in deionized water prior to sterilization can minimize or eliminate the dependence on water content.

[0421] Examples 141 to 146 Polymer discs were prepared using the RMMs listed in Table 25 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted, dried discs (labeled "Dry" in Table 25, corresponding to 0 percent humidity). The average refractive index, Abbe number, water content, tan delta, and storage modulus are shown in Table 25. Standard deviations are listed in parentheses. Some discs were then hydrated in deionized water at 37°C for two weeks, after which the physical and mechanical properties were measured (labeled "Hydrated" in Table 25). Other discs were then stored at ambient temperature under controlled relative humidity (25% or 45% relative humidity) for 24 hours, after which the physical and mechanical properties were measured to determine the effect of relative humidity on the physical properties (labeled "RH25 or RH45" in Table 25).

[0422] [Table 26]

[0423] Examples 141-146 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. For Examples 141-143, samples equilibrated at 25% or 45% relative humidity exhibited lower tan δmax and E' compared to the corresponding dry materials, suggesting that these physical properties depend on water content and, therefore, on post-lens manufacturing conditions, such as drying conditions and relative humidity. Equilibration in deionized water prior to sterilization can minimize or eliminate the dependence on water content.

[0424] Examples 147 to 151 Polymer discs were prepared using the RMMs listed in Table 26 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 inch Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. The average refractive index and Abbe number are listed in Table 26. Standard deviations are listed in parentheses. Some discs were then hydrated in deionized water at 37°C for 2 weeks, after which the water content was measured (labeled "Hydrated" in Table 26).

[0425] [Table 27]

[0426] Examples 147-151 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 147-151 also exhibited low water content (about 1.2-1.6 weight percent), which may provide dimensional stability for implantable ophthalmic devices.

[0427] Examples 152 to 154 Polymer discs were prepared using the RMMs listed in Table 27 using a standard cure and demold procedure (SCDEP) and then extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted, dried discs (labeled "Dry" in Table 27, corresponding to 0 percent humidity). Standard deviations are listed in parentheses. Some discs were then hydrated in deionized water at 37°C for two weeks, after which the water content was measured (labeled "Hydrated" in Table 27).

[0428] [Table 28]

[0429] Examples 152-154 exhibited high refractive indices (greater than 1.51) and Abbe numbers (greater than 50), making these materials ideal for ophthalmic devices such as intraocular lenses. Examples 147-151 also exhibited low water content (about 1.2-1.6 weight percent) that may provide dimensional stability to implantable ophthalmic devices.

[0430] Examples 155-160 (Prophecy) Polymer discs were prepared by thermally curing the RMMs listed in Table 28 at 60-80°C for 2-24 hours and then demolded using the standard demolding procedure (SCDEP). The amount of AIBN was varied to control polymerization rate and reaction time. The polymer discs were extracted with acetonitrile (AAEP). The extracted discs were vacuum dried at 85°C (<1 in. Hg) to constant weight and then stored at room temperature under nitrogen gas in a glove box until analysis. For each example, the refractive index, Abbe number, tan delta, and storage modulus were determined for the extracted and dried discs. Some discs were then hydrated in deionized water at 37°C for 2 weeks, after which their physical and mechanical properties were measured. Other discs were then stored at ambient temperature under controlled relative humidity (25% or 45% relative humidity) for 24 hours, after which their physical and mechanical properties were measured to determine the effect of relative humidity on the physical properties.

[0431] [Table 29]

[0432] Examples 161-162 (Silicone Hydrogel Contact Lenses) A reactive monomer mixture was formed by mixing the reactive components listed in Table 29 with diluent DO, resulting in a weight percent of 68.65 weight percent of the reactive components and a weight percent of DO of 31.35 weight percent. These formulations were filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (approximately 40 mmHg). Approximately 75 μL of the reactive mixture was dispensed onto a FC made with a 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box containing a nitrogen gas atmosphere and less than approximately 0.2 percent oxygen gas. A BC made from a 90:10 (w / w) Z:TT blend was then placed onto the FC. The target spherical power of the mold design was nominally minus 1 diopter. The mold was allowed to equilibrate in the glove box for a minimum of 12 hours before dispensing. The pallets, each containing eight mold assemblies, were transferred into an adjacent glove box maintained at approximately 65°C, and the lenses were placed in the tray at approximately 2 mW / cm 2 The lenses were cured from the top and bottom for a total of 10 minutes using 435 nm LED light with an intensity of 1000 uF. The lenses were manually removed with most of the lens still attached to the FC, and released by suspending them in approximately 1 liter of 70 percent IPA for approximately 1 hour. They were then extracted once with fresh 70% (v / v) aqueous IPA for 30 minutes, hydrated for 60 minutes with deionized water, followed by two 30-minute changes of deionized water, and then equilibrated twice with packing solution for 30 minutes. The lenses were stored in vials in the packing solution. Those skilled in the art will appreciate that the exact lens demolding process, with respect to the concentration of the aqueous isopropanol, the number of washes with each solvent, and the duration of each step, can vary depending on the lens formulation and mold material. The objective of the lens demolding process is to demold all of the lenses without damage and transition from a diluent-swollen network to a packing solution-swollen hydrogel. For each example, the physical and mechanical properties of the lenses were measured and reported in Table 29.

[0433] [Table 30]

[0434] The silicone hydrogel contact lenses of Examples 161 and 162 exhibited a good balance of physical and mechanical properties making them suitable for contact lens wear.

[0435] Examples 163 to 164 (Hydrogel Contact Lenses) A reactive monomer mixture was formed by mixing the reactive components listed in Table 30 with the diluent BAGE, where the weight percent of the reactive components was 68.65 weight percent and the weight percent of DO was 31.35 weight percent. These formulations were filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (approximately 40 mmHg). Approximately 75 μL of the reactive mixture was dispensed onto a FC made with a 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box containing a nitrogen gas atmosphere and less than approximately 0.2 percent oxygen gas. A BC made from a 90:10 (w / w) Zeonor / TT blend was then placed onto the FC. The target spherical power of the mold design was nominally minus 1 diopter. The mold was allowed to equilibrate in the glove box for a minimum of 12 hours before dispensing. Each pallet containing eight mold assemblies was transferred into an adjacent glove box maintained at approximately 65°C, and the lenses were exposed to approximately 2 mW / cm at the tray position. 2The lenses were cured from the top and bottom using 435 nm LED light with an intensity of 1000 nm for a total of 10 minutes. The resulting lenses were manually removed from the molds and then immersed in 70% (v / v) aqueous IPA (approximately 1 hour), extracted once with 70% (v / v) aqueous IPA for 30 minutes, and hydrated with deionized water for 60 minutes; however, the lenses became cloudy. As a result, the lenses were immersed overnight in 75% aqueous IPA, followed by extractions with 50% (v / v) aqueous IPA for 60 minutes, 30% aqueous IPA for 60 minutes, and 15% aqueous IPA for 60 minutes, followed by four extractions with deionized water for 30 minutes each. The lenses were stored in vials in packaging solution. Those skilled in the art will appreciate that the exact lens demolding process, with respect to the concentration of aqueous isopropanol, the number of washes with each solvent, and the duration of each step, can vary depending on the lens formulation and mold material. The objective of the lens demolding process is to demold all of the lenses without damage and to transition them from a diluent-swollen network to a packing solution-swollen hydrogel. For each example, the physical and mechanical properties of the lenses were measured and are reported in Table 30.

[0436] [Table 31]

[0437] The hydrogel contact lenses of Examples 163 and 164 exhibited a good balance of physical and mechanical properties making them suitable for contact lens wear.

[0438] Examples 165 to 168 (Silicone Hydrogel Contact Lenses) Reactive monomer mixtures were prepared consisting of 80 weight percent of the formulation listed in Table 31 and 20 weight percent of diluent DO. The reactive monomer mixtures were individually filtered under pressure through 3 μm filters using stainless steel syringes.

[0439] The formulation was degassed at ambient temperature by applying a vacuum (40 Torr) for 20 minutes. Next, in a glove box containing a nitrogen gas atmosphere and less than about 0.1-0.2 percent oxygen gas, approximately 75 μL of the reactive mixture was dispensed at room temperature using an Eppendorf pipette onto a FC made with a 90:10 (w / w) Zeonor / TT blend. A BC made from a 90:10 (w / w) Z:PP blend was then placed on the FC. The molds were allowed to equilibrate in the glove box for a minimum of 12 hours before dispensing. Each pallet containing eight mold assemblies was transferred into an adjacent glove box maintained at 60°C, and the lenses were placed in the tray position for 2 minutes at approximately 1.6 mW / cm. 2 Then use a 435 nm LED light with an intensity of approximately 3.3 mW / cm at the tray position for 8 min. 2 The compositions were either photocured from the top and bottom (Examples 165 and 167) or heat cured at 60°C for 15-17 hours in an oven with a nitrogen gas atmosphere and less than about 0.1-0.2 percent oxygen gas (Examples 166 and 168).

[0440] With most of the lens still attached to the FC, the lens was manually removed from the mold and released by floating the lens in approximately 1 liter of 70 percent IPA for approximately 1 hour, followed by a 30-minute soak in fresh 50 percent IPA, a 30-minute soak in fresh 25 percent IPA, two 30-minute soaks in fresh DIW, and finally two 30-minute soaks in packing solution. The lens was equilibrated and stored in borate buffered packing solution. Those skilled in the art will appreciate that the exact lens demolding process, with respect to the concentration of the aqueous isopropanol, the number of washes with each solvent, and the duration of each step, can vary depending on the lens formulation and mold material. The objective of the lens demolding process is to release all of the lens without damage and transition from a diluent-swollen network to a packing solution-swollen hydrogel. For each example, the physical and mechanical properties of the lens were measured and reported in Table 31.

[0441] [Table 32]

[0442] The silicone hydrogel contact lenses of Examples 165-168 exhibited a good balance of physical and mechanical properties. One skilled in the art could optimize the formulation to reduce haze and modulus, for example, by adjusting the concentrations of DMAOEMA, HEMA, and EGDMA, and / or by using a different crosslinker, and / or by changing the diluent and / or its concentration.

[0443] Example 169 A reactive monomer mixture was prepared consisting of 80 weight percent of the formulation listed in Table 32 and 20 weight percent of diluent DO. The reactive monomer mixture was filtered under pressure through a 3 μm filter using a stainless steel syringe.

[0444] The resulting formulation was degassed at ambient temperature by applying a vacuum (40 Torr) for 20 minutes. Then, in a glove box with a nitrogen gas atmosphere and less than 0.1-0.2 percent oxygen gas, approximately 75 μL of the reactive mixture was dispensed into a FC made from Zeonor at room temperature using an Eppendorf pipette. A BC made from a 90:10 (w / w) Z:PP blend was then placed on the FC. The molds were allowed to equilibrate in the glove box for a minimum of 12 hours before dispensing. Pallets containing eight mold assemblies each were transferred to a convection oven set at 75°C in an adjacent glove box with a nitrogen gas atmosphere and less than about 0.1-0.2 percent oxygen gas, and the lenses were heat-cured for 60 minutes.

[0445] With most of the lens still attached to the FC, the lens was manually removed from the mold and released by floating the lens in approximately 1 liter of 70 percent IPA for approximately 1 hour, followed by a 30-minute soak in fresh 50 percent IPA, a 30-minute soak in fresh 25 percent IPA, two 30-minute soaks in fresh DIW, and finally two 30-minute soaks in packing solution. The lens was equilibrated and stored in borate buffered packing solution. Those skilled in the art will appreciate that the exact lens demolding process, with respect to the concentration of aqueous isopropanol, the number of washes with each solvent, and the duration of each step, can vary depending on the lens formulation and mold material. The objective of the lens demolding process is to release all of the lens without damage and transition from a diluent-swollen network to a packing solution-swollen hydrogel. For each example, the physical and mechanical properties of the lens were measured and reported in Table 32.

[0446] [Table 33]

[0447] The silicone hydrogel contact lens of Example 169 exhibited a good balance of physical and mechanical properties. One skilled in the art can optimize the formulation to reduce haze and modulus, for example, by adjusting the concentrations of DMAOEMA, HEMA, and EGDMA, and / or by using a different crosslinker, and / or by changing the diluent and / or its concentration.

[0448] Example 170 (Homopolymer Network) Polymer discs were fabricated using a reactive monomer mixture consisting of 98 weight percent DMAOEMA, 1.9 weight percent EGDMA, and 0.1 weight percent Omnirad 1870 using a standard cure, demold, and extraction procedure (SCDEP), with the following exceptions to the cure, extraction, and hydration conditions: (1) the discs were heated to approximately 1.6 mW / cm at the tray position. 2The resin was light-cured at 60°C from the top and bottom for 2 minutes using 435 nm LED light with an intensity of approximately 3.3 mW / cm at the tray position. 2 (2) the discs were extracted with DIW (25 mL per disc) three times for 30 minutes; and (3) the discs were equilibrated in the packing solution. The water content was measured using the contact lens test method and found to be 58.5 weight percent. The polymer network swelled approximately 27 percent based on the difference between the wet and dry lens diameters.

[0449] Example 171 (Prophetic Homopolymer) 18.4 grams (92.1 mmol) of OPEA, 24.8 grams (92.1 mmol) of DAOEA, or 20.0 grams (92.1 mmol) of DHOEMA, and 40 milligrams (0.2 mmol) of AIBN were added to a 1-L reactor and dissolved in approximately 250 mL of 50:50 (v / v) aqueous methanol solution. The solution was degassed by bubbling nitrogen gas through the system at room temperature for approximately 15 minutes. The reaction mixture was heated at 60-62°C under a nitrogen atmosphere for approximately 12 hours and then cooled to room temperature. The solvent was evaporated under reduced pressure. Acetone was added to the residue. The resulting mixture was heated to 62°C for 12 hours with constant stirring, after which the mixture was cooled to room temperature. After standing at room temperature for 2 hours, an insoluble solid precipitated. The acetone was decanted and discarded. The crude product is rinsed in acetone for an additional 2 hours with stirring at room temperature. The acetone is decanted and discarded. The homopolymer is then dried under vacuum at 60-65 °C to constant weight and characterized by NMR spectroscopy (chemical composition) and gel permeation or size exclusion chromatography (molecular weight and molecular weight distribution).

[0450] Example 172 (Prophetic Copolymer) 20.0 grams (92.1 mmol) of DHOEMA, 18.4 grams (92.1 mmol) of OPEA, and 40 milligrams (0.2 mmol) of AIBN were added to a 1-liter reactor and dissolved in approximately 250 mL of a 50:50 (volume / volume) combination of aqueous methanol and another suitable aqueous organic solvent. The molar ratio of the monomers can be varied. The solution was degassed by bubbling nitrogen gas through the system for approximately 15 minutes at room temperature. The reaction mixture was heated at 60-62°C for approximately 12 hours under a nitrogen atmosphere and then cooled to room temperature. The solvent was evaporated under reduced pressure. Acetone was added to the residue. The resulting mixture was heated to 62°C for 12 hours with constant stirring, after which the mixture was cooled to room temperature. After 2 hours at room temperature, an insoluble solid precipitated. The acetone was decanted and discarded. The crude product was rinsed in acetone for an additional 2 hours with stirring at room temperature. The acetone is decanted and discarded. The copolymer is then vacuum dried at 60-65 °C to constant weight and characterized by NMR spectroscopy (chemical composition) and gel permeation size exclusion chromatography (molecular weight and molecular weight distribution).

[0451] [Embodiment] (1) A composition prepared by free radical polymerization of a reactive monomer mixture, the reactive monomer mixture comprising: a) a compatibilizing monomer selected from the group consisting of a pendant carbamate monomer having a chemical structure of Formula I, a pendant amide monomer having a chemical structure of Formula II, and combinations thereof; P g -L-OCONR 1 R 2 Formula I P g -L-CONR 1 R 2 Formula II, In the formula, P g is a polymerizable group, L is a linking group, and R 1 and R 2is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; and b) a cross-linking agent; c) ethylene glycol dicyclopentenyl ether (meth)acrylate, A composition wherein the concentration of the ethylene glycol dicyclopentenyl ether (meth)acrylate in the reactive monomer mixture, excluding any diluents, is 20 weight percent or greater, and the composition exhibits a refractive index of at least 1.45 and an Abbe number of at least 39. (2) The composition of claim 1, wherein the polymerizable group of the compatibilizing monomer is a (meth)acrylate and the linking group of the compatibilizing monomer is an unsubstituted alkylene group. (3) The compatibilizing monomer is selected from the group consisting of Formula III, Formula IV, and combinations thereof: [ka] In the formula, R 3 is H or methyl. (4) The compatibilizing monomer is 2-((methylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((ethylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((propylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((hexylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((octylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((octylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((nonylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((decylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((undecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((dodecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tridecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tetradecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentadecylcarbamoyl )oxy)ethyl (meth)acrylate, 2-((hexadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl (meth)acrylate, 2-oxo-2-(tridecylamino)ethyl (meth)acrylate,The composition of embodiment 3, wherein the hydroxyl group is selected from the group consisting of 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl (meth)acrylate, 2-(dimethylamino)-2-oxoethyl methacrylate, and combinations thereof. (5) The composition of claim 4, wherein the compatibilizing monomer is selected from the group consisting of 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, and combinations thereof.

[0452] 6. The composition of claim 5, wherein the compatibilizing monomer is selected from the group consisting of 2-((butylcarbamoyl)oxy)ethyl acrylate, 2-oxo-2-(pentylamino)ethyl acrylate, and combinations thereof. (7) The crosslinking agent is tricyclo[5.2.1.0 2,6]Decanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecadiodiol di(meth)acrylate 7. The composition of any one of embodiments 1-6, wherein the diol is selected from the group consisting of 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, glycerol tri(meth)acrylate, triallyl cyanurate, methylene bis(meth)acrylamide, poly(ethylene glycol) di(meth)acrylate, and any combination thereof. (8) The crosslinking agent is tricyclo[5.2.1.0 2,6 8. The composition of embodiment 7, wherein the acrylate or acrylate-coated acrylate is selected from the group consisting of decanedimethanol diacrylate, ethylene glycol dimethacrylate, and combinations thereof. (9) The crosslinking agent is tricyclo[5.2.1.0 2,6 9. The composition of embodiment 8, wherein the acrylate is decanedimethanol diacrylate. (10) The composition according to any one of the preceding embodiments, wherein the ethylene glycol dicyclopentenyl ether (meth)acrylate is ethylene glycol dicyclopentenyl ether acrylate.

[0453] (11) The composition of any one of the preceding embodiments, further comprising an aliphatic alkyl (meth)acrylate monomer, wherein the alkyl group contains 1 to 20 carbon atoms. (12) The composition of embodiment 11, wherein the fatty alkyl (meth)acrylate is n-hexyl acrylate. (13) The composition of embodiment 12, wherein the reactive monomer mixture comprises n-hexyl acrylate in an amount of about 0.01 to about 20 weight percent, about 1 to 20 weight percent, about 1 to about 15 weight percent, or about 1 to about 10 weight percent. (14) The composition of any one of the preceding embodiments, further comprising a hydroxyalkyl (meth)acrylate monomer, wherein the hydroxyalkyl group contains 1 to 20 carbon atoms. (15) The composition of embodiment 14, wherein the hydroxyalkyl (meth)acrylate monomer is 4-hydroxybutyl acrylate.

[0454] (16) The composition of embodiment 15, wherein the reactive monomer mixture comprises 4-hydroxybutyl acrylate in an amount of about 0.01 to about 25 weight percent, about 1 to 20 weight percent, about 5 to about 20 weight percent, or about 5 to about 15 weight percent. (17) The composition of any one of embodiments 1 to 16, further comprising a free radical polymerization initiator. 18. The composition of claim 17, wherein the free radical polymerization initiator is a photoinitiator. 19. The composition of claim 18, wherein the photoinitiator is a bisacylphosphine oxide initiator. (20) The composition of embodiment 19, wherein the bisacylphosphine oxide initiator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0455] (21) The composition of any one of embodiments 17-20, wherein the reactive monomer mixture comprises the free radical polymerization initiator in an amount of from about 0.01 weight percent to about 5 weight percent, from about 0.1 weight percent to about 3 weight percent, from about 0.1 weight percent to about 2 weight percent, from about 0.1 weight percent to about 1 weight percent, or from about 0.2 weight percent to about 0.6 weight percent. (22) The composition of any one of the preceding embodiments, wherein the reactive monomer mixture further comprises at least one UV absorbing compound. (23) The composition of any one of embodiments 1 to 22, wherein the reactive monomer mixture further comprises at least one UV / HEV absorbing compound. 24. The composition of claim 23, wherein the UV / HEV absorbing compound is selected from the group consisting of 2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate, 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 3-(3-(tert-butyl)-5-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenyl)propyl methacrylate, or any combination thereof. 25. The composition of claim 24, wherein the UV / HEV absorbing compound is 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate.

[0456] 26. The composition of any one of embodiments 23-25, wherein the reactive monomer mixture comprises the UV / HEV absorbing compound in an amount of from about 0.01 weight percent to about 5 weight percent, from about 0.05 weight percent to about 3 weight percent, from about 0.1 weight percent to about 3 weight percent, from about 0.1 weight percent to about 2 weight percent, from about 0.1 weight percent to about 1 weight percent, or from about 0.1 weight percent to about 0.5 weight percent. (27) The composition of any one of embodiments 1 to 26, further comprising a hydrophilic component selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof. 28. The composition of claim 27, wherein the hydrophilic component is selected from the group consisting of poly(ethylene glycol) methacrylate, poly(ethylene glycol) phenyl ether acrylate, and combinations thereof. (29) The composition of any one of the preceding embodiments, wherein the reactive monomer mixture comprises the compatibilizing monomer in an amount of from about 0.01 weight percent to about 55 weight percent, from about 1 weight percent to about 40 weight percent, from about 5 weight percent to about 35 weight percent, from about 10 weight percent to about 30 weight percent, or from about 20 weight percent to about 30 weight percent. 30. The composition of any one of embodiments 1 to 29, wherein the reactive monomer mixture comprises the crosslinker in an amount of from about 0.1 weight percent to about 10 weight percent, from about 0.1 weight percent to about 5 weight percent, from about 0.5 weight percent to about 3 weight percent, or from about 1 weight percent to about 3 weight percent.

[0457] (31) The composition of any one of the preceding embodiments, wherein the reactive monomer mixture comprises the ethylene glycol dicyclopentenyl ether (meth)acrylate in an amount of from about 25 weight percent to about 95 weight percent, from about 30 weight percent to about 75 weight percent, from about 40 weight percent to about 65 weight percent, or from about 45 weight percent to about 60 weight percent. (32) The composition of any one of the preceding embodiments, wherein the reactive monomer mixture further comprises at least one diluent. (33) The composition of any one of embodiments 1 to 32, wherein the composition has a refractive index of at least 1.45 and an Abbe number of at least 45; the composition has a refractive index of at least 1.48 and an Abbe number of at least 48; the composition has a refractive index of at least 1.49 and an Abbe number of at least 49; the composition has a refractive index of at least 1.50 and an Abbe number of at least 50; the composition has a refractive index of at least 1.51 and an Abbe number of at least 51; or the composition has a refractive index of at least 1.52 and an Abbe number of at least 52. (34) The composition of any one of the preceding embodiments, wherein the composition exhibits a water content of from about 0.01 weight percent to about 15 weight percent, from about 0.1 weight percent to about 10 weight percent, from about 0.5 weight percent to about 5 weight percent, from about 0.5 weight percent to about 3 weight percent, or from about 1 weight percent to about 2 weight percent. (35) The composition of any one of embodiments 1 to 34, wherein the composition exhibits a storage modulus of about 1 MPa to about 100 MPa, about 10 MPa to about 90 MPa, about 20 MPa to about 80 MPa, about 30 MPa to about 80 MPa, or about 40 MPa to about 80 MPa.

[0458] (36) An ophthalmic device comprising the composition according to any one of embodiments 1 to 35. (37) The ophthalmic device of embodiment 36, wherein the ophthalmic device comprises an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert. (38) The ophthalmic device of embodiment 37, wherein the ophthalmic device is an intraocular lens. (39) The ophthalmic device of embodiment 38, wherein the intraocular lens is coated. (40) A method for making an ophthalmic device, comprising: a. providing a composition according to any one of embodiments 1-35; b. forming an ophthalmic device.

[0459] (41) A method for making an ophthalmic device, comprising: a. Preparing a blank from the composition of any one of embodiments 1 to 35; b. machining an ophthalmic device from said blank. (42) A method for making an ophthalmic device, comprising: a. A method comprising molding the device from the composition of any one of embodiments 1-35. (43) A method for making an ophthalmic device, comprising: a. providing the composition of any one of embodiments 1-35 in a mold assembly; b. forming an ophthalmic device; c. Removing the ophthalmic device from the mold assembly. (44) A method for making an ophthalmic device, comprising: a. providing the composition of any one of embodiments 1-35 in a mold assembly; b. forming an ophthalmic device by a photopolymerization reaction; c. Removing the ophthalmic device from the mold assembly. (45) The photopolymerization reaction includes illuminating the mold assembly from the top and the bottom with 435 nanometer light emitting diodes having an intensity profile: a.5mW / cm 2 for 20 minutes (2.5 mW / cm 2 Top and 2.5mW / cm 2 bottom) b. 10 mW / cm 2 for 20 minutes (5 mW / cm 2 Top and 5mW / cm 2 bottom) c.20mW / cm 2 for 20 minutes (10 mW / cm 2 Top and 10mW / cm 2 bottom); and d.30mW / cm 2 for 30 minutes (15 mW / cm 2 Top and 15mW / cm 2 45. The method of embodiment 44, wherein the base is a tubular member.

[0460] (46) The method of any one of embodiments 39 to 45, further comprising extracting the ophthalmic device with a solvent. 47. The method of claim 46, wherein the solvent is selected from the group consisting of acetonitrile, isopropanol, and an aqueous solution of acetonitrile or isopropanol. (48) The method of any one of embodiments 40 to 47, further comprising hydrating the extracted ophthalmic device with at least one aqueous solution. (49) The method of any one of embodiments 40 to 48, further comprising a step of sterilizing the ophthalmic device. (50) The method of embodiment 49, further comprising irradiating the ophthalmic device using a femtosecond two-photon laser either before or after sterilization.

[0461] (51) The method of embodiment 50, wherein the irradiating step is performed on an implanted ophthalmic device. (52) The method of any one of embodiments 40 to 51, wherein the ophthalmic device is selected from the group consisting of an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert. (53) The method of embodiment 52, wherein the ophthalmic device is an intraocular lens. (54) A composition prepared by free radical polymerization of a reactive monomer mixture, said reactive monomer mixture comprising: a) 24 to 28 weight percent 2-((butylcarbamoyl)oxy)ethyl acrylate; b) 10 weight percent 4-hydroxybutyl acrylate; c) 1.5 weight percent tricyclo[5.2.1.0 2,6 ]Decanedimethanol diacrylate; d) 0.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; e) 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; f) 55 to 59 weight percent ethylene glycol dicyclopentenyl ether acrylate; and g) 3 to 6 weight percent n-hexyl acrylate; The concentrations of ethylene glycol dicyclopentenyl ether acrylate and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and the storage modulus is between 1 megapascal and 100 megapascals. (55) A composition prepared by free radical polymerization of a reactive monomer mixture, said reactive monomer mixture comprising: a) 16 to 18 weight percent 2-oxo-2-(decylamino)ethyl (meth)acrylate; b) 10 weight percent 4-hydroxybutyl acrylate; c) 1.5 weight percent tricyclo[5.2.1.02,6 ]Decanedimethanol diacrylate; d) 0.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; e) 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; f) 65 to 67 weight percent ethylene glycol dicyclopentenyl ether acrylate; and g) 5 to 7 weight percent n-hexyl acrylate; wherein the concentrations of 2-oxo-2-(decylamino)ethyl (meth)acrylate, ethylene glycol dicyclopentenyl ether acrylate, and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and the storage modulus is between 1 megapascal and 100 megapascals.

[0462] (56) An ophthalmic device manufactured from the composition according to any one of embodiments 54 to 55. (57) The ophthalmic device described in embodiment 56, wherein the ophthalmic device is an intraocular lens. (58) The ophthalmic device of embodiment 57, wherein the intraocular lens is coated. (59) Formula II, P g -L-CONR 1 R 2 wherein P g is a polymerizable group, L is a linking group, and R 1 and R 2 are independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups. (60) The compound of embodiment 59, wherein the polymerizable group is a (meth)acrylate and the linking group is an unsubstituted alkylene group.

[0463] (61) The compound has a chemical structure represented by formula IV: [ka] In the formula, R 3 is H or methyl. (62) The compound is selected from the group consisting of 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2 -Oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl (meth)acrylate, 2-oxo-2- 62. The compound of embodiment 61, wherein the compound is selected from the group consisting of (tridecylamino)ethyl (meth)acrylate, 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl (meth)acrylate, and 2-(dimethylamino)-2-oxoethyl methacrylate. (63) A method for producing any of the compounds according to embodiments 59 to 62, the method comprising: a. reacting a primary or secondary amine with methyl glycolate to form an N-alkyl-2-hydroxyacetamide or an N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide; b. reacting said N-alkyl-2-hydroxyacetamide or said N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide with (meth)acryloyl chloride. (64) A composition prepared by free radical polymerization of a reactive monomer mixture comprising any of the compounds described in embodiments 59 to 62. (65) The reactive monomer mixture j) a cross-linking agent; and k) ethylene glycol dicyclopentenyl ether (meth)acrylate; l) aliphatic alkyl (meth)acrylate monomers; m) hydroxyalkyl (meth)acrylate monomers; n) free radical polymerization initiators; o) at least one UV absorbing compound; p) at least one UV / HEV absorbing compound; q) a hydrophilic component selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof; and r) at least one diluent.

[0464] (66) An ophthalmic device comprising any one of the compositions described in embodiments 64 to 65. (67) The ophthalmic device of embodiment 66, wherein the ophthalmic device is selected from the group consisting of an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert. (68) The ophthalmic device of embodiment 67, wherein the ophthalmic device is a contact lens.

Claims

1. 1. A composition made by free radical polymerization of a reactive monomer mixture, said reactive monomer mixture comprising: a) a compatibilizing monomer selected from the group consisting of a pendant carbamate monomer having a chemical structure of Formula I, a pendant amide monomer having a chemical structure of Formula II, and combinations thereof; P ｇ -L-OCONR １ R ２ Formula I P ｇ -L-CONR １ R ２ Formula II In the formula, P ｇ is a polymerizable group, L is a linking group, and R １ and R ２ is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups; and b) a cross-linking agent; and c) ethylene glycol dicyclopentenyl ether (meth)acrylate, a concentration of the ethylene glycol dicyclopentenyl ether (meth)acrylate in the reactive monomer mixture, excluding any diluents, is 20 weight percent or greater, and the composition exhibits a refractive index of at least 1.45 and an Abbe number of at least 39.

2. The composition of claim 1 , wherein the polymerizable group of the compatibilizing monomer is a (meth)acrylate and the linking group of the compatibilizing monomer is an unsubstituted alkylene group.

3. The compatibilizing monomer is selected from the group consisting of Formula III, Formula IV, and combinations thereof: 【Chemistry 1】 In the formula, R ３ The composition of claim 2 , wherein is H or methyl.

4. The compatibilizing monomers include 2-((methylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((ethylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((propylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((hexylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((octylcarbamoyl)oxy)ethyl (meth)acrylate, 2- ... 2-((octylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((nonylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((decylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((undecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((dodecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tridecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((tetradecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((pentadecylcarbamoyl )oxy)ethyl (meth)acrylate, 2-((hexadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-((heptadecylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl (meth)acrylate, 2-oxo-2-(tridecylamino)ethyl (meth)acrylate,The composition of claim 3, wherein the methyl group is selected from the group consisting of 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl (meth)acrylate, 2-(dimethylamino)-2-oxoethyl methacrylate, and combinations thereof.

5. 5. The composition of claim 4, wherein the compatibilizing monomer is selected from the group consisting of 2-((butylcarbamoyl)oxy)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, and combinations thereof.

6. 6. The composition of claim 5, wherein the compatibilizing monomer is selected from the group consisting of 2-((butylcarbamoyl)oxy)ethyl acrylate, 2-oxo-2-(pentylamino)ethyl acrylate, and combinations thereof.

7. The crosslinking agent is tricyclo[5.2.1.0 ２，６ ] decanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecadiodiol di(meth)acrylate 7. The composition of claim 1, wherein the diol is selected from the group consisting of acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, glycerol tri(meth)acrylate, triallyl cyanurate, methylene bis(meth)acrylamide, poly(ethylene glycol) di(meth)acrylate, and any combination thereof.

8. The crosslinking agent is tricyclo[5.2.1.0 ２，６ 8. The composition of claim 7, wherein the acrylate is selected from the group consisting of decanedimethanol diacrylate, ethylene glycol dimethacrylate, and combinations thereof.

9. The crosslinking agent is tricyclo[5.2.1.0 ２，６ ] decanedimethanol diacrylate.

10. The composition of claim 1 , wherein the ethylene glycol dicyclopentenyl ether (meth)acrylate is ethylene glycol dicyclopentenyl ether acrylate.

11. The composition of claim 1 further comprising an aliphatic alkyl (meth)acrylate monomer, the alkyl group containing 1 to 20 carbon atoms.

12. The composition of claim 11, wherein the fatty alkyl (meth)acrylate is n-hexyl acrylate.

13. 13. The composition of claim 12, wherein the reactive monomer mixture comprises n-hexyl acrylate in an amount of about 0.01 to about 20 weight percent, about 1 weight percent to 20 weight percent, about 1 weight percent to about 15 weight percent, or about 1 weight percent to about 10 weight percent.

14. The composition of claim 1 further comprising a hydroxyalkyl (meth)acrylate monomer, wherein the hydroxyalkyl group contains from 1 to 20 carbon atoms.

15. The composition of claim 14, wherein the hydroxyalkyl (meth)acrylate monomer is 4-hydroxybutyl acrylate.

16. 16. The composition of claim 15, wherein the reactive monomer mixture comprises 4-hydroxybutyl acrylate in an amount from about 0.01 to about 25 weight percent, from about 1 weight percent to 20 weight percent, from about 5 weight percent to about 20 weight percent, or from about 5 weight percent to about 15 weight percent.

17. The composition of claim 1 further comprising a free radical polymerization initiator.

18. 18. The composition of claim 17, wherein the free radical polymerization initiator is a photoinitiator.

19. 20. The composition of claim 18, wherein the photoinitiator is a bisacylphosphine oxide initiator.

20. 20. The composition of claim 19, wherein the bisacylphosphine oxide initiator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

21. 21. The composition of any one of claims 17-20, wherein the reactive monomer mixture comprises the free radical polymerization initiator in an amount from about 0.01 weight percent to about 5 weight percent, from about 0.1 weight percent to about 3 weight percent, from about 0.1 weight percent to about 2 weight percent, from about 0.1 weight percent to about 1 weight percent, or from about 0.2 weight percent to about 0.6 weight percent.

22. The composition of claim 1 , wherein the reactive monomer mixture further comprises at least one UV absorbing compound.

23. The composition of claim 1 , wherein the reactive monomer mixture further comprises at least one UV / HEV absorbing compound.

24. 24. The composition of claim 23, wherein the UV / HEV absorbing compound is selected from the group consisting of 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate, 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 3-(3-(tert-butyl)-5-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenyl)propyl methacrylate, or any combination thereof.

25. 25. The composition of claim 24, wherein the UV / HEV absorbing compound is 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate.

26. 26. The composition of any one of claims 23-25, wherein the reactive monomer mixture comprises the UV / HEV absorbing compound in an amount from about 0.01 weight percent to about 5 weight percent, from about 0.05 weight percent to about 3 weight percent, from about 0.1 weight percent to about 3 weight percent, from about 0.1 weight percent to about 2 weight percent, from about 0.1 weight percent to about 1 weight percent, or from about 0.1 weight percent to about 0.5 weight percent.

27. 10. The composition of claim 1, further comprising a hydrophilic component selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof.

28. 28. The composition of claim 27, wherein the hydrophilic component is selected from the group consisting of poly(ethylene glycol) methacrylate, poly(ethylene glycol) phenyl ether acrylate, and combinations thereof.

29. 10. The composition of claim 1, wherein the reactive monomer mixture comprises the compatibilizing monomer in an amount from about 0.01 weight percent to about 55 weight percent, from about 1 weight percent to about 40 weight percent, from about 5 weight percent to about 35 weight percent, from about 10 weight percent to about 30 weight percent, or from about 20 weight percent to about 30 weight percent.

30. 10. The composition of claim 1, wherein the reactive monomer mixture comprises the crosslinker in an amount of from about 0.1 weight percent to about 10 weight percent, from about 0.1 weight percent to about 5 weight percent, from about 0.5 weight percent to about 3 weight percent, or from about 1 weight percent to 3 weight percent.

31. 10. The composition of claim 1, wherein the reactive monomer mixture comprises the ethylene glycol dicyclopentenyl ether (meth)acrylate in an amount from about 25 weight percent to about 95 weight percent, from about 30 weight percent to about 75 weight percent, from about 40 weight percent to about 65 weight percent, or from about 45 weight percent to about 60 weight percent.

32. The composition of claim 1 , wherein the reactive monomer mixture further comprises at least one diluent.

33. 10. The composition of claim 1, wherein the composition has a refractive index of at least 1.45 and an Abbe number of at least 45; wherein the composition has a refractive index of at least 1.48 and an Abbe number of at least 48; wherein the composition has a refractive index of at least 1.49 and an Abbe number of at least 49; wherein the composition has a refractive index of at least 1.50 and an Abbe number of at least 50; wherein the composition has a refractive index of at least 1.51 and an Abbe number of at least 51; or wherein the composition has a refractive index of at least 1.52 and an Abbe number of at least 52.

34. 10. The composition of claim 1, wherein the composition exhibits a water content of from about 0.01 weight percent to about 15 weight percent, from about 0.1 weight percent to about 10 weight percent, from about 0.5 weight percent to about 5 weight percent, from about 0.5 weight percent to about 3 weight percent, or from about 1 weight percent to about 2 weight percent.

35. 10. The composition of claim 1, wherein the composition exhibits a storage modulus of from about 1 megapascal to about 100 megapascals, from about 10 megapascals to about 90 megapascals, from about 20 megapascals to about 80 megapascals, from about 30 megapascals to about 80 megapascals, or from about 40 megapascals to about 80 megapascals.

36. An ophthalmic device comprising the composition of claim 1.

37. 37. The ophthalmic device of claim 36, wherein the ophthalmic device comprises an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert.

38. The ophthalmic device of claim 37 , wherein the ophthalmic device is an intraocular lens.

39. The ophthalmic device of claim 38, wherein the intraocular lens is coated.

40. 1. A method for making an ophthalmic device, comprising: a. providing the composition of claim 1; b. forming an ophthalmic device.

41. 1. A method for making an ophthalmic device, comprising: a. preparing a blank from the composition of claim 1; b. machining an ophthalmic device from said blank.

42. 1. A method for making an ophthalmic device, comprising: A method comprising: a. molding said device from the composition of claim 1.

43. 1. A method for making an ophthalmic device, comprising: a. providing the composition of claim 1 in a mold assembly; b. forming an ophthalmic device; c) removing the ophthalmic device from the mold assembly.

44. 1. A method for making an ophthalmic device, comprising: a. providing the composition of claim 1 in a mold assembly; b. forming an ophthalmic device by photopolymerization; c) removing the ophthalmic device from the mold assembly.

45. The photopolymerization reaction includes illuminating the mold assembly from the top and the bottom with 435 nanometer light emitting diodes having an intensity profile: a. 5 mW / cm ２ for 20 minutes (2.5 mW / cm ２ Top and 2.5 mW / cm ２ bottom) b. 10 mW / cm ２ for 20 minutes (5 mW / cm ２ Top and 5mW / cm ２ bottom) c. 20 mW / cm ２ for 20 minutes (10 mW / cm ２ Top and 10 mW / cm ２ bottom); and d. 30 mW / cm ２ for 30 minutes (15 mW / cm ２ Top and 15 mW / cm ２ 45. The method of claim 44, wherein the base comprises a base.

46. 41. The method of claim 40, further comprising extracting the ophthalmic device with a solvent.

47. 47. The method of claim 46, wherein the solvent is selected from the group consisting of acetonitrile, isopropanol, and an aqueous solution of acetonitrile or isopropanol.

48. 41. The method of claim 40, further comprising hydrating the extracted ophthalmic device with at least one aqueous solution.

49. 41. The method of claim 40, further comprising sterilizing the ophthalmic device.

50. 50. The method of claim 49, further comprising irradiating the ophthalmic device using a femtosecond two-photon laser either before or after sterilization.

51. 51. The method of claim 50, wherein the irradiating step is performed on an implanted ophthalmic device.

52. 41. The method of claim 40, wherein the ophthalmic device is selected from the group consisting of an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert.

53. 53. The method of claim 52, wherein the ophthalmic device is an intraocular lens.

54. 1. A composition made by free radical polymerization of a reactive monomer mixture, said reactive monomer mixture comprising: a) 24 to 28 weight percent 2-((butylcarbamoyl)oxy)ethyl acrylate; b) 10 weight percent 4-hydroxybutyl acrylate; c) 1.5 weight percent tricyclo[5.2.1.0 ２，６ ] decanedimethanol diacrylate; d) 0.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; e) 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; f) 55 to 59 weight percent ethylene glycol dicyclopentenyl ether acrylate; and g) 3 to 6 weight percent n-hexyl acrylate; wherein the concentrations of ethylene glycol dicyclopentenyl ether acrylate and n-hexyl acrylate vary, but the components of the reactive monomer mixture total 100 weight percent; the composition exhibits a refractive index of at least 1.50 and an Abbe number of at least 50, and the storage modulus is from 1 megapascal to 100 megapascals.

55. 1. A composition made by free radical polymerization of a reactive monomer mixture, said reactive monomer mixture comprising: a) 16 to 18 weight percent 2-oxo-2-(decylamino)ethyl (meth)acrylate; b) 10 weight percent 4-hydroxybutyl acrylate; c) 1.5 weight percent tricyclo[5.2.1.0 ２，６ ] decanedimethanol diacrylate; d) 0.2 weight percent 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)propyl methacrylate; e) 0.45 weight percent bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; f) 65 to 67 weight percent ethylene glycol dicyclopentenyl ether acrylate; and g) 5 to 7 weight percent n-hexyl acrylate; 1. A composition comprising: 2-oxo-2-(decylamino)ethyl (meth)acrylate, ethylene glycol dicyclopentenyl ether acrylate, and n-hexyl acrylate in varying concentrations, the components of the reactive monomer mixture totaling 100 weight percent; the composition exhibiting a refractive index of at least 1.50 and an Abbe number of at least 50, and the storage modulus is from 1 megapascal to 100 megapascals.

56. An ophthalmic device manufactured from the composition of any one of claims 54-55.

57. The ophthalmic device of claim 56, wherein the ophthalmic device is an intraocular lens.

58. 58. The ophthalmic device of claim 57, wherein the intraocular lens is coated.

59. Formula II, P ｇ -L-CONR １ R ２ wherein P ｇ is a polymerizable group, L is a linking group, and R １ and R ２ is independently selected from H, alkyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, amidoalkyl, cycloalkyl, cycloalkyl(alkyl), heterocycloalkyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl groups.

60. 60. The compound of claim 59, wherein the polymerizable group is a (meth)acrylate and the linking group is an unsubstituted alkylene group.

61. The compound has the chemical structure shown by Formula IV: 【Chemistry 2】 In the formula, R ３ is H or methyl.

62. The compounds include 2-oxo-2-(methylamino)ethyl (meth)acrylate, 2-oxo-2-(ethylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, ...propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(pentylamino)ethyl (meth)acrylate, 2-oxo-2-(hexylamino)ethyl (meth)acrylate, 2-oxo-2-(propylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl (meth)acrylate, 2-oxo-2-(butylamino)ethyl ( -oxo-2-(heptylamino)ethyl (meth)acrylate, 2-oxo-2-(octylamino)ethyl (meth)acrylate, 2-oxo-2-(nonylamino)ethyl (meth)acrylate, 2-oxo-2-(decylamino)ethyl (meth)acrylate, 2-oxo-2-(undecylamino)ethyl (meth)acrylate, 2-oxo-2-(dodecylamino)ethyl (meth)acrylate, 2-oxo-2 62. The compound of claim 61, wherein the compound is selected from the group consisting of 2-(tridecylamino)ethyl (meth)acrylate, 2-oxo-2-(tetradecylamino)ethyl (meth)acrylate, 2-oxo-2-((3-methoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((3-ethoxypropyl)amino)ethyl (meth)acrylate, 2-oxo-2-((cyclohexylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-(benzylamino)ethyl (meth)acrylate, 2-oxo-2-(phenethylamino)ethyl (meth)acrylate, 2-oxo-2-((thiophen-2-ylmethyl)amino)ethyl (meth)acrylate, 2-oxo-2-((2,3-dihydroxypropyl)amino)ethyl (meth)acrylate, and 2-(dimethylamino)-2-oxoethyl methacrylate.

63. 60. A method of making the compound of claim 59, said method comprising: a. reacting a primary or secondary amine with methyl glycolate to form an N-alkyl-2-hydroxyacetamide or an N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide; b) reacting said N-alkyl-2-hydroxyacetamide or said N-alkyl(R')-N-alkyl(R'')-2-hydroxyacetamide with (meth)acryloyl chloride.

64. 60. A composition prepared by free radical polymerization of a reactive monomer mixture comprising the compound of claim 59.

65. The reactive monomer mixture a) a crosslinker; and b) ethylene glycol dicyclopentenyl ether (meth)acrylate; c) aliphatic alkyl (meth)acrylate monomers; d) hydroxyalkyl (meth)acrylate monomers; e) a free radical polymerization initiator; f) at least one UV absorbing compound; g) at least one UV / HEV absorbing compound; h) a hydrophilic component selected from the group consisting of poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether (meth)acrylate, and combinations thereof; and 65. The composition of claim 64, further comprising at least one of: i) at least one diluent.

66. An ophthalmic device comprising any of the compositions of claims 64-65.

67. 67. The ophthalmic device of claim 66, wherein the ophthalmic device is selected from the group consisting of an intraocular lens, a phakic intraocular lens, a contact lens, a corneal inlay, a corneal outlay, or a corneal insert.

68. 68. The ophthalmic device of claim 67, wherein the ophthalmic device is a contact lens.

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