Polymers and methods for ophthalmic applications

Abstract

To provide a new family of high refractive index polymers particularly suitable for foldable intraocular lens applications.SOLUTION: A copolymer is provided which comprises: (a) a monomer comprising an aromatic, carbazole or naphthyl moiety, carbazole, naphthalene or a naphthyl group; (b) a first hydrophilic monomer; and (c) a second hydrophilic monomer.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross - Reference to Related Applications This application is a continuation - in - part of U.S. Patent Application No. 13 / 411,836, filed on March 5, 2012, the disclosure of which is hereby incorporated by reference in its entirety.

[0002] Field Novel materials particularly useful for ophthalmic applications and methods for their production and use are disclosed herein. More specifically, relatively flexible, optically transparent, foldable high refractive index materials particularly suitable for use in the production of intraocular lenses, contact lenses and other ophthalmic implants, and methods for their manufacture and use are disclosed.

Background Art

[0003] Since the 1940s, intraocular lens (IOL) shaped optical devices have been utilized as replacements for diseased or damaged natural crystalline lenses. In most cases, for example in the case of cataracts, when the diseased or damaged natural lens is surgically removed, the intraocular lens is implanted into the eye. For decades, the preferred material for making the above - mentioned intraocular lenses has been poly(methyl methacrylate) (PMMA), a hard, glass - like polymer. In recent years, more flexible and pliable IOLs have gained popularity due to their ability to be compressed, folded, rotated, or deformed. Such more flexible IOLs can be deformed before insertion through an incision in the eye's cornea. Once inserted into the eye, the IOL returns to its original, pre-folded shape due to the memory properties of the flexible material. The aforementioned more flexible and pliable IOLs can be implanted into the eye through an incision less than 4.0 mm, i.e., much smaller than the 5.5 - 8.0 mm incisions required for implanting stiffer IOLs. Larger incisions are required for stiffer IOLs because the lens needs to be inserted through a corneal incision slightly larger than the diameter of the optic portion of the inflexible IOL. Thus, the popularity of stiffer intraocular lenses in the market has stalled because it has been found that larger incisions are associated with an increased incidence of postoperative complications such as the induction of astigmatism. With recent advancements in small incision cataract surgery, the development of flexible, foldable polymer materials suitable for use in artificial IOLs has become even more important. Generally, these materials fall into one of three categories: hydrogels, silicones, and low glass transition temperature acrylates.

[0004] A more recent advancement in IOL implantation is the use of an IOL injector to implant the IOL into the eye. See US 2007 / 0060925 to Pynson, "Preloaded IOLS Injector and Methods"; US 2005 / 0222578 to Vaquero, "IOL Injector"; and "Preloaded IOL Injector" to Vaquero et al.; each of these patent documents is hereby incorporated by reference in its entirety for reference purposes. Unfortunately, injector implantation of IOLs generally proceeds more smoothly (i.e., with lower surgical difficulty) the stiffer, and thus generally more manageable (dealt with), the IOL is. Therefore, for surgical purposes, a stiffer lens is recommended. Usually, this means implanting a polymer lens with a hydration lower than full hydration. As is well known, the post-implant hydration of an IOL can, in some cases, unexpectedly change the refractive index (RI) of the lens. This change burdens the surgeon and injectable IOL implantation with uncertainty regarding surgical outcomes. Generally, high water content hydrogel materials have a relatively low refractive index and make the hydrogel material less desirable than other materials with respect to the minimum incision size. Low refractive index materials require a thicker IOL optic to obtain a given refractive power. Silicone materials have a higher refractive index than high water content hydrogels but tend to open too quickly after being placed in the folded position within the eye. The too-rapid opening of the folded lens can potentially damage the corneal endothelium and / or rupture the natural lens capsule and associated zonules.

[0005] Low glass transition temperature acrylic materials are desirable because these acrylic materials typically have a high refractive index and open more slowly and adjustably than silicone materials, for example, when inserted into the lens capsule. Unfortunately, low glass transition temperature acrylic materials initially contain little or no water and absorb puddles of water in vivo, resulting in light reflection or "glistening". Furthermore, due to the temperature sensitivity of the acrylic polymer memory, it is difficult to achieve ideal folding and opening characteristics. U.S. Patent No. 5,480,950, issued on January 2, 1996, discloses a high refractive index hydrogel material having a hydration equilibrium water content (「EWC」) of at least 57% for use in the manufacture of IOLs. The high refractive index hydrogel material is a crosslinked polymer made from a mixture of N-vinylpyrrolidone, 4-vinylpyrimidine and vinylpyridine, having an equilibrium water content of up to 90% and a refractive index of 1.560 to 1.594 in the dry state. The IOL as described is not implanted in the hydrated state. Rather, the IOL is dried, folded and stretched and implanted, and hydrated in situ. The refractive index in the hydrated state when used in the eye is not presented. U.S. Patent Application Publication No. 2002 / 0049290 relates to a high refractive index (RI) ophthalmic hydrogel material. U.S. Patent No. 5,693,095, issued on December 2, 1997, discloses a high refractive index low water content IOL material. The material taught in this particular patent is an acrylic material having at least 150% elongation. An IOL made from a material having such elongation properties does not crack, tear or split when folded. However, such low water content acrylic materials have been found to be less biocompatible than other materials when manufactured and used as IOL devices.

[0006] In the past decade, hydrophobic polymers have been used with some success in the manufacture of IOLs. The ophthalmic industry has accepted this type of polymer as having good physical properties and acceptable biocompatibility in the intraocular environment. However, current IOLs made from conventional hydrophobic polymers are experiencing poor optical stability (e.g., glistening, optical artifacts) and low refractive indices in the ocular fluid. The formation of undesirable particles and deposits in the bulk of the hydrophobic polymer is due to uncontrolled water sorption and subsequent phase separation. Conventional homopolymers currently used to produce copolymers with high RI (>1.51) absorb variable amounts of dispersed water, resulting in phase separation, haze and glistening. Currently, there are no foldable high RI IOL polymers that are resistant to glistening and deposit formation. Compositions known to be resistant to the formation of glistening require pre-implant hydration. This restricts foldability, incision size, and packaging prior to loading, leading to a rapid selection of the IOL packaging method. More importantly, there are no IOLs manufactured from polymers having an EWC value in the range of about 3 wt% to about 15 wt%. Without wishing to be bound by any theory, this group of polymers is believed to be more resistant to glistening. In the present invention, there are provided compositions, polymers, and methods for manufacturing non-glistening IOLs having an EWC of 5 - 15%. The advantages of the compositions and methods disclosed herein relate to post-implant hydratable or hydrophilic IOL polymers, particularly to reducing or eliminating the uncertainty of surgical outcomes when performing implantation using an IOL injector.

Summary of the Invention

[0007] The present invention is a novel group of high RI polymers particularly suitable for foldable IOL applications, but not limited thereto. The material is optically stable in the ocular fluid and resistant to the formation of unwanted optical artifacts. The above unique properties of the copolymers disclosed herein are obtained by incorporating hydrophilic polymers into a highly hydrophobic polymer matrix, enabling the copolymers to have a specific EWC in the range of about 3 wt% to about 15 wt%, preferably in the range of about 4 wt% to about 10 wt%. Furthermore, the limited amount of water to be absorbed is well distributed and well dispersed within the matrix, preventing the macrophase separation observed in prior art compositions. The result is an optically transparent material having stable optical properties.

[0008] It is well understood that such compositions result in IOLs having refractive optical powers that change upon implantation within the eye. Another aspect disclosed herein is to experimentally predict the change in refractive optical power by measuring the hydrated IOL diopters prior to drying and sterilization for packaging. Accordingly, in this further aspect, a method for measuring the refractive index / diopter after implantation of an intraocular lens is disclosed herein. In this method, the lens, typically (but not always) an intraocular lens, is in a substantially dehydrated state after manufacture and is made sufficiently manipulable for implantation into the eye through a corneal incision, for example, by an IOL injector. The lens after manufacture is hydrated, for example, by soaking the lens in saline, for example, at room temperature for 24 hours. The diopter of the hydrated lens is measured while the lens polymer is in a hydrated state equivalent to the hydrated state the lens will obtain when implanted into the eye. Thereafter, the diopter of the IOL is measured outside the eye in its hydrated state. Thereafter, the lens is at least partially sufficiently dehydrated, sterilized, and stored in a substantially dry state until the lens is sufficiently manipulable for implantation, for example, by an IOL injector. The implanted IOL is then implanted into the eye through a corneal incision using an injector. Thereafter, the implanted and partially dehydrated IOL is hydrated within the eye until it equilibrates to substantially the same refractive index (and thus diopter) obtained by measurement while the IOL was hydrated prior to implantation. In this implementation of the invention, the refractive index of the hydrated IOL after implantation is obtained with nearly 100% certainty while also obtaining all the advantages of an injector or injector-based IOL implantation method.

[0009] In one aspect, a method for measuring the post-implantation diopter of a pre-implantation lens, comprising: providing an intraocular lens (IOL) comprising a polymer whose stiffness and refractive index depend on its hydrated state; Exposing the lens before implantation to a hydration solution for a length of time sufficient to hydrate the IOL polymer to a state of hydration that is substantially equivalent to the state of hydration that the IOL polymer will obtain after implantation; Measuring the diopter value of the substantially hydrated lens; Partially dehydrating the lens to enhance its handling characteristics; Implanting the partially dehydrated IOL into the eye; and Allowing the partially dehydrated lens to hydrate in the eye after implantation until it obtains a diopter value that is substantially the same as the diopter value of the lens measured before implantation The method is disclosed herein, including the above steps.

[0010] Intraocular lenses ("IOLs"), contact lenses, and novel copolymers that may be particularly adapted for other ophthalmic and optical applications are disclosed herein. The compositions and IOLs manufactured from the copolymers disclosed herein have a very high refractive index and can be machined or molded at approximately room temperature. The IOLs disclosed herein can be folded and inserted through a small incision and used to replace the defective natural lens of the eye without the need for further processing or hydration. A particular advantage of the materials and copolymers disclosed herein is the unique hybrid properties of the materials and copolymers that prevent unconstrained water sorption. A foldable ophthalmic lens material having an adjustable and uniform relatively high water content and an unexpectedly high refractive index, and being particularly suitable for use as an intraocular lens (IOL) or other ophthalmic device, such as, but not limited to, contact lenses, artificial corneal grafts, and corneal rings or inlays, is a first area of the compositions, methods, and polymers disclosed herein. In one embodiment, the disclosure relates to a copolymer composition comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, carbazole, naphthalene or a naphthyl group and a limited amount of monomers including a hydrophobic monomer. The carbazole and / or naphthyl moiety monomers, in addition to the comonomers, increase the refractive index of the comonomers. Monomers having a surface tension generally in the range of 50 dynes / cm or less are used to produce a highly hydrophobic matrix. A hydrophilic polymer is added to produce a hydrophilic phase for suppressed water sorption (in the method described below).

[0011] In one embodiment, the disclosure relates to a copolymer composition comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, carbazole, naphthalene or a naphthyl group, a first hydrophilic monomer and a second hydrophilic monomer. In yet another embodiment, the disclosure relates to a copolymer comprising (a) vinylnaphthalene; (b) 2-(2-ethoxyethoxy)ethyl acrylate; (c) hydroxyethyl acrylate; and (d) a crosslinking agent. In still another embodiment, the disclosure relates to a copolymer comprising (a) a monomer containing an aromatic, carbazole or naphthyl moiety, carbazole, naphthalene or a naphthyl group and (b) one or more hydrophilic monomers (the one or more hydrophilic monomers being 68% to 77% by mass of the composition). In yet another embodiment, the disclosure relates to a copolymer comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, carbazole, naphthalene or a naphthyl group and one or more hydrophilic monomers (the composition being at least 60% by mass of hydrophilic monomers). In yet another embodiment, the disclosure relates to a copolymer comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, carbazole, naphthalene or a naphthyl group and one or more hydrophilic monomers (the copolymer comprising 60% to 80% by mass of hydrophilic monomers).

[0012] In yet another embodiment, the disclosure relates to a copolymer comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, a monomer having a carbazole, naphthalene or naphthyl group, and one or more hydrophilic monomers (the copolymer comprises 70% to 80% by weight of the hydrophilic monomer). In yet another embodiment, the disclosure relates to a copolymer comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, a monomer having a carbazole, naphthalene or naphthyl group, and one or more hydrophilic monomers (the copolymer comprises 70% to 75% by weight of the hydrophilic monomer). In yet another embodiment, the disclosure relates to a copolymer comprising an aromatic monomer and / or a carbazole and / or a naphthyl moiety, a monomer having a carbazole, naphthalene or naphthyl group, and one or more hydrophilic monomers (the copolymer comprises 75% to 80% by weight of the hydrophilic monomer). Accordingly, an advantage of the compositions, polymers and methods disclosed herein is to provide a biocompatible IOL having a high refractive index. Another advantage of the compositions, polymers and methods disclosed herein is to provide an IOL material having a high refractive index and suppressed water sorption. Yet another advantage of the compositions, polymers and methods of the present invention is to provide a method that enables accurate targeting of the power of the lens in vivo. Yet another advantage of the compositions, polymers and methods disclosed herein is to provide an IOL material that is relatively easy to manufacture. Advantages of the compositions, polymers and methods disclosed herein are: (1) a polymer less prone to abnormal vision; (2) a polymer having excellent biocompatibility; (3) a polymer having good optical transparency; (4) a polymer that is damage-resistant and protects against biological contamination.

[0013] There is no abnormal photopsia. The polymers disclosed herein have a high water content and a low refractive index compared to hydrophobic acrylic IOLs, minimizing glare, external and internal reflections, and other undesirable visual phenomena. Excellent biocompatibility. The polymers disclosed herein appear to have minimal impact on the blood-aqueous barrier and could be an excellent choice for patients with uveitis and diabetes. Good optical transparency. The polymers disclosed herein have high anti-calcification properties and will not be associated with glistening or foreign bodies as seen in previous hydrophobic acrylic IOLs. Damage resistance during insertion. The polymers disclosed herein are resistant to folding marks and forceps damage. Protection from biological contamination. Bacteria adhere less readily to this lens material than to polymethylmethacrylate (PMMA) or hydrophobic acrylic IOLs. These and other objects and advantages, some of which are described in detail and some not, will become apparent from the following detailed description and the claims.

Best Mode for Carrying Out the Invention

[0014] For all aspects of the Periodic Table of the Elements, reference is made to the Periodic Table of the Elements published by CRC Press in 1990 and copyrighted. Also, for any radical(s), the radical(s) will be those reflected in this Periodic Table of the Elements using the IUPAC system for numbering the radical(s). Conversely, unless otherwise indicated, unless implicitly indicated from the context or unless otherwise generally indicated in the art, all parts and percentages are by mass and all test methods are as of the filing date of this disclosure. For the purposes of U.S. patent practice, the contents of cited patents, patent applications or publications are incorporated by reference in their entirety (or their equivalent U.S. variations are so incorporated) with respect to the disclosure of synthetic methods, product and process designs, polymers, catalysts, definitions (to the extent not inconsistent with the definitions specifically set forth in this disclosure) and general knowledge in the art. The numerical ranges in this disclosure are approximate values, and thus, unless otherwise specified, values outside the range may be included. If there is a separation of at least two units between the smaller value and the larger value, the numerical range includes all values in increments of one unit, including the lower and upper limits. As an example, when a composition, physical property, or other characteristic, such as molecular weight, viscosity, melt index, etc., is from 100 to 1,000, it means all individual values, such as 100, 101, 102, etc., and sub-ranges, such as 100 - 144, 155 - 170, 197 - 200, etc., are explicitly listed. For ranges having values less than 1 or having a fraction greater than 1 (e.g., 1.1, 1.5, etc.), as appropriate, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1. For ranges having single-digit numbers less than 10 (e.g., 1 - 5), one unit is typically considered to be 0.1. These are merely examples, although intended, and all possible combinations of numerical values between the lowest and highest values listed should be considered to be explicitly disclosed in this disclosure. Numerical ranges are indicated within the scope of this disclosure, particularly for the mass percentages of components within the scope of the compositions disclosed herein.

[0015] The term "about" as used herein in connection with a numerical range changes the range slightly by extending the boundaries above and below the recited numerical values. In one embodiment, the term "about" is used herein to change the numerical values above and below the explicitly stated value by a variation of 10%. Thus, about 50% includes the range from 45% to 55%. As used with respect to compounds, unless otherwise indicated, the singular form includes all isomers, and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). The terms "compound" and "complex" are used interchangeably to represent organic compounds, inorganic compounds, and organometallic compounds. The term "atom" represents the smallest component of an element, regardless of its ionic state, i.e., whether it has a charge or partial charge or is bonded to other atoms.

[0016] The terms "comprising", "including", "having", and the like do not mean excluding the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all processes recited in claims by use of the term "comprising" may include, unless the contrary is expressly stated, one or more additional steps, apparatus or component parts and / or materials of the component parts. In contrast, the term "consisting essentially of" excludes other components, steps, or procedures from the scope of the following description, except for those that are not essential to the operability. The term "consisting of" excludes components, steps, or procedures not specifically described or recited. The term "or" means not only individually recited one by one but also combinations thereof, unless otherwise specified. The terms "composition" and similar terms mean a mixture or blend of two or more components. "Copolymer" means a polymer prepared from two different monomers and a polymer prepared from more than two different monomers, such as a terpolymer, a tetrapolymer, and the like. The term "polymer" (and similar terms) is a high molecular weight compound prepared by reacting (i.e., polymerizing) the same or different types of monomers. "Polymers" include homopolymers and copolymers.

[0017] Materials having a high refractive index are desirable for enabling manufacturers to produce thinner IOLs. A thin IOL or a thin optical IOL is important for enabling surgeons to minimize the incision size. Keeping the surgical incision size to a minimum reduces intraoperative mental trauma and postoperative complications. Thin IOLs are also important for adapting to certain anatomical locations in the eye, such as the anterior chamber and the ciliary sulcus. The IOL may be placed in the anterior chamber to improve vision in both aphakic and phakic eyes, or in the ciliary sulcus to improve vision in phakic eyes. The compositions and polymers disclosed herein have the flexibility necessary to allow them to be folded or deformed so that the IOLs produced therefrom can be introduced into the eye by the smallest possible incision. In one embodiment, the novel material is a copolymer, trimer, tetramer, etc., comprising at least two monomer components: a hydrophobic monomer and a hydrophilic monomer. In one embodiment, a crosslinking agent is generally included. In another embodiment, a UV absorber is included. In one embodiment, the composition comprises a multimer comprising a first monomer having an aromatic, carbazole and / or naphthyl moiety, and the monomer of the aromatic / carbazole / naphthyl moiety is present in the composition at a concentration of at least about 20%, preferably up to 35 - 80%.

[0018] In another embodiment, the composition further comprises a second monomer having a hydrophobic homopolymer, the hydrophobicity being defined as a homopolymer having a surface tension of about 50 dynes / cm or less, and the second monomer is present in the copolymer in an amount of at least about 20% by weight, preferably about 50 - 60% by weight. In yet another embodiment, the composition then comprises at least about 10% by weight of a hydrophilic monomer, preferably about 20 - 30% by weight. The composition then comprises a crosslinkable monomer, and the crosslinkable monomer is present at a concentration within the range of up to about 10% by weight, preferably about 1% - about 8% by weight. In still another embodiment, the disclosure relates to a composition comprising a first monomer having an aromatic, carbazole and / or naphthyl moiety and one or more hydrophilic monomers. In yet another embodiment, the aromatic / carbazole / naphthyl moiety monomer is present in the composition at a concentration of at least about 20%. In still another embodiment, the aromatic / carbazole / naphthyl moiety monomer is present in the composition at a concentration of about 35 - about 80%. In yet another embodiment, the disclosure relates to a copolymer comprising monomers having an aromatic, carbazole and / or naphthyl moiety, a first hydrophilic monomer and a second hydrophilic monomer.

[0019] In yet another embodiment, the disclosure relates to a copolymer comprising a monomer having an aromatic, carbazole and / or naphthyl moiety, wherein the aromatic / carbazole / naphthyl moiety monomer is present in the composition at a concentration of about 20 wt% to about 30 wt%; and one or more hydrophilic monomers of about 70 wt% to about 80 wt%. In another embodiment, the copolymer further comprises a crosslinking agent. In still another embodiment, the copolymer further comprises a UV absorber. In yet another embodiment, the copolymer further comprises an initiator including, but not limited to, azobisisobutyronitrile (AIBN). In yet another embodiment, the disclosure relates to a copolymer comprising a monomer having an aromatic, carbazole and / or naphthyl moiety, a first hydrophilic monomer, a second hydrophilic monomer, a UV absorber, a crosslinking agent and an initiator. In another embodiment, the one or more hydrophilic monomers comprise about 50 wt% to about 80 wt% of the copolymer, about 55 wt% to about 80 wt% of the copolymer, about 60 wt% to about 80 wt% of the copolymer, about 65 wt% to about 80 wt% of the copolymer, about 70 wt% to about 80 wt% of the copolymer or about 75 wt% to about 80 wt% of the copolymer. In yet another embodiment, the one or more hydrophilic monomers comprise about 50 wt% to about 75 wt% of the copolymer, about 50 wt% to about 70 wt% of the copolymer, about 50 wt% to about 65 wt% of the copolymer, about 50 wt% to about 60 wt% of the copolymer or about 50 wt% to about 55 wt% of the copolymer.

[0020] In yet another embodiment, the one or more hydrophilic monomers comprise from about 62% to about 80% by weight of the copolymer, from about 64% to about 80% by weight of the copolymer, from about 66% to about 80% by weight of the copolymer, from about 68% to about 80% by weight of the copolymer, from about 72% to about 80% by weight of the copolymer, from about 74% to about 80% by weight of the copolymer, from about 76% to about 80% by weight of the copolymer or from about 78% to about 80% by weight of the copolymer. In yet another embodiment, the one or more hydrophilic monomers comprise from about 66% to about 78% by weight of the copolymer, from about 66% to about 76% by weight of the copolymer, from about 66% to about 74% by weight of the copolymer, from about 66% to about 72% by weight of the copolymer, from about 66% to about 70% by weight of the copolymer or from about 66% to about 68% by weight of the copolymer. In yet another embodiment, the one or more hydrophilic monomers comprise from about 67% to about 78% by weight of the copolymer, from about 68% to about 78% by weight of the copolymer, from about 69% to about 78% by weight of the copolymer, from about 70% to about 78% by weight of the copolymer, from about 71% to about 78% by weight of the copolymer, from about 72% to about 78% by weight of the copolymer, from about 73% to about 78% by weight of the copolymer, from about 74% to about 78% by weight of the copolymer, from about 57% to about 78% by weight of the copolymer, from about 76% to about 78% by weight of the copolymer or from about 77% to about 78% by weight of the copolymer. In yet another embodiment, the one or more hydrophilic monomers comprise from about 67% to about 75% by weight of the copolymer, from about 68% to about 75% by weight of the copolymer, from about 69% to about 75% by weight of the copolymer, from 70% to about 75% by weight of the copolymer, from about 71% to about 75% by weight of the copolymer, from about 72% to about 75% by weight of the copolymer, from about 73% to about 75% by weight of the copolymer or from about 74% to about 75% by weight of the copolymer.

[0021] Suitable hydrophilic monomers (i.e., monomers whose homopolymers are hydrophilic according to the compositions, methods, and polymers disclosed herein) include, but are not limited to, 2-hydroxy-ethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, N-ornithine acrylamide, N-(2-hydroxypropyl) acrylamide, polyethylene glycol acrylate, polyethylene glycol methacrylate, N-vinyl pyrrolidone, N-phenyl acrylamide, dimethylaminopropyl methacrylamide, acrylic acid, benzyl methacrylamide, 4-hydroxybutyl methacrylate, glycerol monomethacrylate, glycerol monoacrylate, 2-sulfoethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, furfuryl acrylate, furfuryl methacrylate, and methylthioethyl acrylamide. Any of the above-mentioned hydrophilic monomers can be the first or second hydrophilic monomer in the composition.

[0022] Suitable hydrophobic monomers (i.e., monomers whose homopolymers are hydrophobic according to the compositions, methods, and polymers disclosed herein) include, but are not limited to, lauryl methacrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-decyl acrylate, n-decyl methacrylate, hexyl acrylate, hexyl methacrylate, stearyl acrylate, stearyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, vinyl laurate, vinyl stearate, 1-hexadecyl acrylate, 1-hexadecyl methacrylate, n-myristyl acrylate, n-myristyl methacrylate, n-dodecyl methacrylamide, butyl acrylate, n-butyl methacrylate, isooctyl acrylate, isotridecyl acrylate, isooctyl methacrylate, and isotridecyl methacrylate.

[0023] Suitable crosslinking agents include, but are not limited to, for example, ethylene glycol dimethacrylate (EGDMDA), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and poly(ethylene glycol) dimethacrylate, among which ethylene glycol dimethacrylate is preferred. Suitable initiators include, but are not limited to, for example, azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1'-azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, di(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl) peroxydicarbonate, t-amyl peroxyneodecanoate, and t-butyl peroxyacetate, among which 2,2'-azobis(isobutyronitrile) is preferred.Suitable ultraviolet absorbers include, but are not limited to, for example, beta-(4-benzotriazolyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2'-methacryloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3''-methacryloyloxypropyl)phenyl]-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[3''-dimethylvinylsilylpropoxy-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3'-allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3''-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3'-tert-butyl-2'-hydroxy-5'-(3''-methacryloyloxy-propoxy)phenyl]-5-chlorobenzotriazole. Among them, beta-(4-benzotriazolyl-3-hydroxyphenoxy)ethyl acrylate is a preferred ultraviolet absorber.

[0024] In one embodiment, the crosslinking agent may be present in about 0.1% to about 10%, about 0.3% by mass to about 10% by mass, about 0.5% by mass to about 10% by mass, about 1% by mass to about 10% by mass, about 2% by mass to about 10% by mass, about 3% by mass to about 10% by mass, about 4% by mass to about 10% by mass, about 5% by mass to about 10% by mass or about 6% by mass to about 10% by mass of the composition. In one embodiment, the crosslinking agent may be present in about 1% by mass to about 5% by mass, about 2% by mass to about 5% by mass, about 3% by mass to about 5% by mass or about 4% by mass to about 5% by mass of the composition. The UV absorber may be optionally added to the copolymer composition. A novel and preferred UV / blue light absorber, namely vinyl anthracene, may be added to the copolymer composition. General UV absorbers such as vinyl benzophenone or vinyl benzotriazole may also be used. In another embodiment, the UV absorber may be present in about 0.1 wt% to about 5 wt%, about 0.2 wt% to about 5 wt%, about 0.4 wt% to about 5 wt%, about 0.6 wt% to about 5 wt%, about 0.8 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 1.5 wt% to about 5 wt%, about 2 wt% to about 5 wt%, about 3 wt% to about 5 wt% or about 4 wt% to about 5 wt% of the composition.

[0025] In yet another embodiment, the disclosure relates to a copolymer comprising (a) a monomer having an aromatic, carbazole and / or naphthyl moiety present in about 18 wt% to about 28 wt% of the composition, (b) a first hydrophilic monomer present in about 39 wt% to about 49 wt% of the composition, and (c) a second hydrophilic monomer present in about 23 wt% to about 33 wt% of the composition. In yet another embodiment, the disclosure relates to a copolymer comprising (a) a monomer having an aromatic, carbazole and / or naphthyl moiety that is at least about 20 wt% of the copolymer, (b) a first hydrophilic monomer that is at least about 40 wt% of the composition, and (c) a second hydrophilic monomer that is at least about 25 wt% of the composition. In yet another embodiment, the disclosure relates to a copolymer comprising (a) monomers having aromatic, carbazole and / or naphthyl moieties including, but not limited to, vinylcarbazole, vinylnaphthalene, 2-vinylnaphthalene, and mixtures thereof; (b) a first hydrophilic monomer of 2-(2-ethoxyethoxy)ethyl acrylate; and (c) a second hydrophilic monomer of hydroxyl acrylate. In yet another embodiment, the copolymer further comprises a UV absorber. In yet another embodiment, the copolymer comprises a crosslinking agent including, but not limited to, ethylene glycol dimethacrylate. In yet another embodiment, the copolymer comprises an initiator including, but not limited to, AIBN.

[0026] In yet another embodiment, the disclosure relates to a copolymer comprising (a) 2-vinylnaphthalene, (b) a first hydrophilic monomer that is 2-(2-ethoxyethoxy)ethyl acrylate, (c) a second hydrophilic monomer that is hydroxyl acrylate, (d) a UV absorber, (e) a crosslinking agent, and (f) an initiator. In yet another embodiment, the disclosure relates to a copolymer comprising (a) 2-vinylnaphthalene that is at least about 20% by weight of the composition, (b) 2-(2-ethoxyethoxy)ethyl acrylate that is a first hydrophilic monomer and at least about 40% by weight of the composition, (c) hydroxyl acrylate that is a second hydrophilic monomer and at least about 25% by weight of the composition, (d) a UV absorber that is at least about 0.5% by weight of the composition, (e) a crosslinking agent that is at least about 2.5% by weight of the composition, and (f) an initiator that is at least about 0.1% by weight of the composition. In yet another embodiment, the disclosure relates to a copolymer comprising a monomer having an aromatic, carbazole and / or naphthyl moiety, a first hydrophilic monomer, and a second monomer having a homopolymer with a glass transition temperature (Tg) of less than 20°C. In yet another embodiment, the disclosure relates to a copolymer comprising (a) a monomer having an aromatic, carbazole, and / or naphthyl moiety present in an amount of about 18 wt% to about 28 wt% of the composition, (b) a first hydrophilic monomer present in an amount of about 39 wt% to about 49 wt% of the composition, and (c) a second monomer having a homopolymer with a Tg of less than 20 °C present in an amount of about 23 wt% to about 33 wt% of the composition.

[0027] In yet another embodiment, the disclosure relates to a copolymer comprising (a) a monomer having an aromatic, carbazole, and / or naphthyl moiety that is at least about 20 wt% of the copolymer, (b) a first hydrophilic monomer that is at least about 40 wt% of the composition, and (c) a second monomer having a homopolymer with a Tg of less than 20 °C that is at least about 25 wt% of the composition. In one embodiment, the copolymer disclosed herein has an EWC in the range of about 5 wt% to about 15 wt%. In one embodiment, the copolymer disclosed herein has an EWC in the range of about 3 wt% to about 15 wt%. In another embodiment, the copolymer disclosed herein has an EWC in the range of about 4 wt% to about 10 wt%. In another embodiment, the copolymer disclosed herein has an EWC in the range of about 5 wt% to about 10 wt%. In one embodiment, the copolymer disclosed herein in the dry state has an EWC in the range of about 5 wt% to about 15 wt%. In one embodiment, the copolymer disclosed herein in the dry state has an EWC in the range of about 3 wt% to about 15 wt%. In another embodiment, the copolymer disclosed herein in the dry state has an EWC in the range of about 4 wt% to about 10 wt%. In another embodiment, the copolymer disclosed herein in the dry state has an EWC in the range of about 5 wt% to about 10 wt%.

[0028] In another embodiment, the compositions and copolymers disclosed herein can be used to manufacture IOLs using techniques known in the art. In one embodiment, the IOL is manufactured using a lathe cutting method. Generally, lathe cutting places the lens material on a rotating mount, and a mechanical cutting device cuts away excess lens material to create a precision cut lens. The lens is then polished and characterized. In another embodiment, the IOL is manufactured using a molding technique. In one embodiment, a comonomer solution is injected into a mold, cured at 60 °C for 4 hours, and post-cured at 100 °C for 4 - 8 hours. The IOL is demolded and extracted with a suitable solvent. In another embodiment, injection molding for contact lenses is performed by heating the lens material to its melting point and then injecting the liquid lens material into a pre-cut mold. When the lens material dries, it solidifies into the shape of the mold, obtaining the exact shape of the lens. After removing the lens, excess material is removed, and after polishing the lens, it is inspected for quality and characterization.

Examples

[0029] Table 1 Examples 1 - 9:

Table 1

[0030] 0.3% by mass of MEB was used in all copolymer compositions. PEA: 2-Phenylethyl acrylate PEMA: 2-Phenylethyl methacrylate POEA: Phenoxyethyl acrylate BA: Benzyl acrylate BMA: Benzyl methacrylate VC: Vinyl carbazole VN: Vinyl naphthalene EHA: 2-Ethylhexyl acrylate LM: Lauryl methacrylate HEMA: Hydroxyethyl methacrylate HEA: Hydroxyethyl acrylate EEEA: 2-(2-Ethoxyethoxy)ethyl acrylate EGDM: Ethylene glycol dimethacrylate MEB: 2-(2'-Methacryloxy-5'-methylphenyl)benzotriazole

[0031] Table 1. General preparation process of the polymers of Examples 1 to 9 The comonomers listed above were mixed in a glass flask using a magnetic stir bar for at least 30 minutes, then sonicated for the following time, and then stirred again for 30 minutes. The inventors have found that sonication for about 30 minutes at 100% output setting in Branson 5510 results in an optically transparent material having suitable optical and physical properties. The monomer solution was degassed with argon and poured into a 15.24 cm × 15.24 cm (6 inch × 6 inch) mold made from glass plates spaced with silicone gaskets. The mold was kept at 60 °C for 6 hours and then post-cured at 100 °C in vacuo for 12 hours. The resulting copolymer is sufficiently hard to be machined at approximately room temperature. The unique aspect of the compositions, methods, and polymers disclosed herein is that the refractive index of these materials is high enough to be thin enough to fold the lens without further processing or hydration. The IOL is machined from the above copolymer to determine the diopter. The IOL is hydrated in distilled water at 50 °C for 3 hours, and the diopter is measured again in the hydrated state. The value obtained is the actual power of the lens to be used for labeling. Alternatively, a mathematical formula associating the diopter of the dry lens with the diopter of the same lens hydrated can be developed from data as described below and used to label the IOL.

[0032] Empirical estimation of in vivo lens diopter Unlike conventional hydrogels where lens hydration results in a significant decrease in diopters due to a decrease in the RI of the polymer upon water absorption, the lenses disclosed herein exhibit a relatively moderate change in diopters upon hydration due to a counterbalancing effect of a small amount of absorbed water and simultaneous steep gradient changes in lens swelling and radius of curvature. Lenses were lathe cut from sheets made from the polymer compositions manufactured according to the above procedure. Ten (10) lenses were selected for each composition. Table 2 below shows the diopters of 20 D lenses before and after hydration made from Polymer Examples 1 - 8.

[0033] Table 2 Examples 1 - 8: [Table 2]

Claims

1. A copolymer comprising: (a) a monomer containing an aromatic, carbazole or naphthyl moiety, a carbazole, naphthalene or naphthyl group; (b) a first hydrophilic monomer; and (c) a second hydrophilic monomer.

2. The copolymer of claim 1 further comprising a crosslinker.

3. The copolymer of claim 1 further comprising an ultraviolet light absorbing material.

4. 2. The copolymer of claim 1, wherein the monomer containing an aromatic, carbazole or naphthyl moiety is vinyl naphthalene or vinyl carbazole.

5. 2. The copolymer of claim 1, wherein the first hydrophilic monomer and the second hydrophilic monomer are selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, N-ornithine acrylamide, N-(2-hydroxypropyl)acrylamide, polyethylene glycol acrylate, polyethylene glycol methacrylate, N-vinylpyrrolidone, N-phenylacrylamide, dimethylaminopropyl methacrylamide, acrylic acid, benzyl methacrylamide, 4-hydroxybutyl methacrylate, glycerol monomethacrylate, glycerol monoacrylate, 2-sulfoethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, furfuryl acrylate, furfuryl methacrylate, and methylthioethyl acrylamide.

6. The copolymer of claim 1 , wherein the first hydrophilic monomer is 2-(2-ethoxyethoxy)ethyl acrylate.

7. 7. The copolymer of claim 6, wherein 2-(2-ethoxyethoxy)ethyl acrylate is from 39% to 49% by weight of the composition.

8. The copolymer of claim 1 , wherein the second hydrophilic monomer is hydroxyethyl acrylate.

9. The copolymer of claim 8, wherein hydroxyethyl acrylate is from 23% to 33% by weight of the composition.

10. The ultraviolet light absorbing material is beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2'-methacryloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3''-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-( ...

4. The copolymer of claim 3, selected from the group consisting of rt-butyl-5'-(3-dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3'-allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'tert'-butyl-2'-hydroxy-5'-(3''-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3'-tert-butyl-2'-hydroxy-5'-(3''-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.

11. The copolymer of claim 3 , wherein the ultraviolet absorbing material is vinyl anthracene or a derivative thereof.

12. (a) vinyl naphthalene; (b) 2-(2-ethoxyethoxy)ethyl acrylate; (c) hydroxyethyl acrylate; and (d) a crosslinker.

13. The copolymer of claim 12 further comprising an ultraviolet light absorbing material.

14. 14. The copolymer of claim 13, wherein vinyl naphthalene is from 18% to 28% by weight of the copolymer; 2-(2-ethoxyethoxy)ethyl acrylate is from 39% to 49% by weight of the copolymer; hydroxyethyl acrylate is from 23% to 33% by weight of the copolymer; said crosslinker is from 2.5% to 3.5% by weight of the copolymer, and said ultraviolet light absorbing material is from 0.5% to 1.5% by weight of the copolymer.

15. 13. The copolymer of claim 12 having an EWC of 5% to 15%.

16. 15. The copolymer of claim 14 having an EWC of 5% to 15%.

17. A copolymer comprising: (a) a monomer containing an aromatic, carbazole or naphthyl moiety, a carbazole, naphthalene or naphthyl group; and (b) one or more hydrophilic monomers, wherein the one or more hydrophilic monomers are 68% to 77% by weight of the composition.

18. 18. The copolymer of claim 17 having an EWC of 5% to 15%.

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