Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/14—Macromolecular materials
  • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
  • A61L27/52—Hydrogels or hydrocolloids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5397—Phosphine oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/24—Homopolymers or copolymers of amides or imides
  • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
  • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
  • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
  • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
  • A61F2/02—Prostheses implantable into the body
  • A61F2/14—Eye parts, e.g. lenses or corneal implants; Artificial eyes
  • A61F2/16—Intraocular lenses
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2430/00—Materials or treatment for tissue regeneration
  • A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
  • G02B1/007—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of negative effective refractive index materials
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
  • G02B1/043—Contact lenses
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
  • G02C7/022—Ophthalmic lenses having special refractive features achieved by special materials or material structures
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
  • G02C7/04—Contact lenses for the eyes

Definitions

• Cataract surgery is commonly performed to replace the natural eye lens that has become opaque.
• Materials that are used to replace the natural crystalline lens must be soft and have excellent flexibility so that, once formed into a lens, they may be folded and passed through an incision which is typically about 2 mm. Furthermore, the material must have excellent transparency and little to no glistening. Having a high refractive index allows for a thinner lens to be used.
• a material with a high Abbe number demonstrates less dispersion. This, in turn, allows for improved optical results and less light scattering. Combining a high refractive index with a high Abbe number provides preferable optical characteristics for a material.
• 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 it is held in its rolled configuration, then released inside the chamber of the eye.
• the elastic properties of the lens cause it to resume 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.
• composition (A) (i) at least one aromatic (meth)acrylate; (ii) at least one hydroxyalkyl (meth)acrylate; (iii) at least one polyamide; and (iv) at least one bis(2-hydroxypropyl (meth)acrylate) terminated polysiloxane crosslinking agent; wherein the composition exhibits a refractive index of at least 1.45 and an Abbe number of at least 39 (“Composition (A)”); or
• composition (B) (i) at least one aromatic (meth)acrylate; (ii) at least one hydroxyalkyl (meth)acrylate; and (iii) at least one bis(2-hydroxypropyl (meth)acrylate) terminated polysiloxane crosslinking agent; wherein the crosslinking agent is present in the reactive monomer mixture in an amount of about 15% to about 22% by weight (“Composition (B)”); or
• composition (C) (i) at least one hydrophobic monomer; (ii) at least one hydroxyl-containing monomer; (iii) at least one crosslinking agent; and (iv) at least one polyamide, wherein the reactive monomer mixture comprises the polyamide in an amount of about 0.10 to about 5.0 weight percent (“Composition (C)”).
• the present disclosure provides a device comprising
• the present disclosure provides a method for making an ophthalmic device, the method comprising the steps of: (a) providing any one of Composition (A), Composition (B), or Composition (C); and (b) forming an ophthalmic device from any of said compositions.
• the presently disclosed subject matter provides a method for making an ophthalmic device, the method comprising: (a) preparing a blank from any one of Composition (A), Composition (B), or Composition (C); and (b) machining an ophthalmic device from the blank.
• the term“reactive monomer mixture” refers to a mixture of components (both reactive and non-reactive) which are mixed together and when subjected to polymerization conditions, form the presently disclosed compositions and ophthalmic devices.
• the reactive mixture may include reactive components such as monomers, macromers, prepolymers, crosslinkers, initiators, diluents, and additional components, including, but not limited to, wetting agents, release agents, dyes, light absorbing compounds, such as UV absorbers, pigments, dyes and photochromic compounds, any of which may be reactive or non-reactive but are capable of being retained within the resulting biomedical device, e.g., an ophthalmic device, as well as active components, including pharmaceutical and nutraceutical compounds, and any diluents.
• concentrations of components of the reactive mixture are given in weight % of all components in the reaction mixture, excluding diluent. When diluents are used their concentrations are given as weight % based upon the amount of all components in the reaction mixture and the diluent.
• the term“(meth)” designates optional methyl substitution.
• a term such as“(meth)acrylates” denotes both methacrylates and acrylates.
• the term“individual” includes humans and non-human vertebrates.
• the term“biomedical device” refers to any article that is designed to be used while either in or on mammalian tissues or fluids, and preferably in or on human tissue or fluids. Examples of these devices include but are not limited to wound dressings, sealants, tissue fillers, drug delivery systems, coatings, adhesion prevention barriers, catheters, implants, stents, and ophthalmic devices such as intraocular implants, intraocular lenses, and contact lenses.
• the biomedical devices may be ophthalmic devices, particularly ophthalmic implants or ophthalmic lenses made from the reactive monomer compositions described herein.
• optical surface includes the surface and glandular epithelia of the cornea, conjunctiva, lacrimal gland, accessory lacrimal glands, nasolacrimal duct and meibomian gland, and their apical and basal matrices, pun eta and adjacent or related structures, including eyelids linked as a functional system by both continuity of epithelia, by innervation, and the endocrine and immune systems.
• ophthalmic device refers to any device which resides in or on the eye or any part of the eye, including the ocular surface. These devices can provide optical correction, cosmetic enhancement, vision enhancement, therapeutic benefit (for example as bandages) or delivery of active components such as pharmaceutical and nutraceutical components, or a combination of any of the foregoing. Examples of ophthalmic devices include but are not limited to lenses, optical and ocular inserts, including but not limited to punctal plugs, and the like. “Lenses” include soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and overlay lenses. The ophthalmic device may comprise an intraocular implant, intraocular lens, or contact lens.
• the term“contact lens” refers to an ophthalmic device that can be placed on the cornea of an individual's eye.
• the contact lens may provide corrective, cosmetic, or therapeutic benefit, including wound healing, the delivery of drugs or nutraceuticals, diagnostic evaluation or monitoring, ultraviolet light absorbing, visible light or glare reduction, or any combination thereof.
• a contact lens can be of any appropriate material known in the art and can be a soft lens, a hard lens, or a hybrid lens containing at least two distinct portions with different physical, mechanical, or optical properties, such as modulus, water content, light transmission, or combinations thereof.
• Intraocular lens refers to a lens implanted in an eye.
• the intraocular lens is implanted in the eye to replace an existing crystalline lens (such as, for example, because the existing lens has been clouded over by a cataract, or as a form of refractive surgery to change the eye's optical power).
• Target macromolecule means the macromolecule being synthesized from the reactive monomer mixture comprising monomers, macromers, prepolymers, crosslinkers, initiators, additives, diluents, and the like.
• polymerizable compound means a compound containing one or more polymerizable groups.
• the term encompasses, for instance, monomers, macromers, oligomers, prepolymers, crosslinkers, and the like.
• the free radical polymerizable groups comprise (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinylamide, and styryl functional groups, and mixtures of any of the foregoing. More preferably, the free radical polymerizable groups comprise
• (meth)acrylates (meth)acrylamides, and mixtures thereof.
• the polymerizable group may be unsubstituted or substituted.
• the nitrogen atom in (meth)acrylamide may be bonded to a hydrogen, or the hydrogen may be replaced with alkyl or cycloalkyl (which themselves may be further substituted).
• A“monomer” is a mono-functional molecule which can undergo chain growth polymerization, and in particular, free radical polymerization, thereby creating a repeating unit in the chemical structure of the target macromolecule. Some monomers have di- functional impurities that can act as crosslinking agents.
• A“hydrophilic monomer” is also a monomer which yields a clear single phase solution when mixed with deionized water at25°C at a concentration of 5 weight percent.
• A“hydrophilic component” is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer which yields a clear single phase solution when mixed with deionized water at 25°C at a concentration of 5 weight percent.
• hydrophobic component is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer which is slightly soluble or insoluble in deionized water at 25°C.
• A“macromolecule” is an organic compound having a number average molecular weight of greater than 1500 Daltons and may be reactive or non-reactive.
• A“polymer” is a target macromolecule composed of the 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; a“terpolymer” is a polymer made from three monomers.
• a “block copolymer” is composed of compositionally different blocks or segments. Diblock copolymers have two blocks. Triblock copolymers have three blocks.“Comb or graft copolymers” are made from at least one macromer.
• A“repeating unit” is the smallest group of atoms in a polymer that corresponds to the polymerization of a specific monomer or macromer.
• An“initiator” is a molecule that can decompose into radicals which can subsequently react with a monomer to initiate a free radical polymerization reaction.
• a thermal initiator decomposes at a certain rate depending on the temperature; typical examples are azo compounds such as I ,G-azobisisobutyronitrile and 4,4’ -azo bis(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 as well as various redox systems.
• a photo-initiator decomposes by a photochemical process; typical examples are derivatives of benzil, benzoin, acetophenone, benzophenone,
• camphorquinone and mixtures thereof as well as various monoacyl and bisacyl phosphine oxides and combinations thereof.
• A“crosslinking agent” is a di-functional or multi-functional monomer or macromer which can undergo free radical polymerization at two or more locations on the molecule, thereby creating branch points and a polymeric network.
• Common examples are ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylene bisacrylamide, triallyl cyanurate, and the like.
• A“prepolymer” is a reaction product of monomers which contains remaining polymerizable groups capable of undergoing further reaction to form a polymer.
• the terms “reactive mixture” and“reactive monomer mixture” refer to the mixture of components (both retained and non-retained) which are mixed together and, when subjected to polymerization conditions, result in formation of a polymeric network as well as biomedical devices, ophthalmic devices, intraocular implants, contact lenses, and intraocular lenses made therefrom.
• the reactive mixture may comprise retained components such as monomers, macromers, prepolymers, crosslinkers, and initiators, additives such as wetting agents, polymers, dyes, light absorbing compounds such as UV absorbers, pigments, photochromic compounds,
• the reactive mixture may also contain non-retained components which are intended to be removed from the device prior to its use, such as diluents. It will be appreciated that a wide range of additives may be added based upon the biomedical device which is made and its intended use. Concentrations of components of the reactive mixture are expressed as weight percentages of all retained components in the reactive mixture, therefore excluding non-retained components such as diluent. When diluents are used, their concentrations are expressed as weight percentages based upon the amount of all components in the reactive mixture (including the diluent).
• “Retained components” are the polymerizable compounds (such as monomers, macromers, oligomers, prepolymers, and crosslinkers) in the reactive mixture, as well as any other components in the reactive mixture which are intended to substantially remain in the polymeric network after polymerization and all work-up steps (such as extraction steps) and packaging steps have been completed. Retained components may be retained in the polymeric network by covalent bonding, hydrogen bonding, electrostatic interactions, the formation of interpenetrating polymeric networks, or any other means.
• Components that are intended to release from the biomedical device once it is in use are still considered“retained components.”
• pharmaceutical or nutraceutical components in a contact lens which are intended to be released during wear are considered“retained components.”
• Components that are intended to be removed from the polymeric network during the manufacturing process are“non-retained components.”
• multi-functional refers to a component having two or more polymerizable groups.
• mono-functional refers to a component having one polymerizable group.
• halogen or“halo” indicate fluorine, chlorine, bromine, and iodine.
• alkyl or“aliphatic” are used interchangeably herein and refer to an optionally substituted linear or branched alkyl group containing the indicated number of carbon atoms. If no number is indicated, then alkyl (including any optional substituents on alkyl) may contain 1 to 16 carbon atoms, including 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, and 16 carbon atoms.
• the alkyl group contains 1 to 10 carbonatoms, including 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 carbon atoms, alternatively 1 to 8 carbonatoms, including 1 , 2, 3, 4, 5, 6, 7, and 8 carbon atoms, alternatively 1 to 6 carbon atoms, including 1 , 2, 3, and 4 carbon atoms, or alternatively 1 to 4 carbon atoms, including 1 , 2, 3, and 4.
• alkyl include methyl, ethyl, propyl, isopropyl, butyl, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, 3 -ethylbutyl, and the like.
• “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 -hydroxy ethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 2,3-dihydroxypentyl, 4- hydroxybutyl, 2-ethyl-4-hydroxyheptyl, 3,4-dihydroxybutyl, and 5-hydroxypentyl.
• Cycloalkyl or“cycloaliphatic” are used interchangeably herein and refer to an optionally substituted cyclic hydrocarbon containing the indicated number of ring carbon atoms. If no number is indicated, then cycloalkyl may contain 3 to 12 ring carbon atoms. Preferred are C 3 -C 8 cycloalkyl groups, C 3 -C 7 cycloalkyl, more preferably C 4 -C 7 cycloalkyl, and still more preferably C5-C6 cycloalkyl. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
• substituents on cycloalkyl include 1 , 2, or 3 groups independently selected from alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, thioalkyl, amido, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof.
• Cycloalkylene means a divalent cycloalkyl group, such as 1 ,2-cyclohexylene, 1 ,3- cyclohexylene, or 1,4- cyclohexylene.
• heterocycloalkyl rings and/or non-aromatic hydrocarbon rings and/or phenyl rings Preferred heterocycloalkyl groups have from 5 to 7 members. More preferred heterocycloalkyl groups have 5 or 6 members.
• Heterocycloalkylene means a divalent heterocycloalkyl group.
• Aryl refers to an optionally substituted aromatic hydrocarbon ring system containing at least one aromatic ring.
• the aryl group contains the indicated number of ring carbon atoms. If no number is indicated, then aryl may contain 6 to 14 ring carbon atoms.
• the aromatic ring may optionally be fused or otherwise attached to other aromatic hydrocarbon rings or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Preferred examples of aryl groups include phenyl.
• substituents on aryl include 1 , 2, or 3 groups independently selected from alkyl, hydroxy, amino, amido, oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof.
• “Arylene” means a divalent aryl group, for example 1 ,2-phenylene, 1 ,3-phenylene, or 1 ,4-phenylene.
• Heteroaryl refers to an aryl ring or ring system, as defined above, in which at least one ring carbon atom has been replaced with a heteroatom selected from nitrogen, oxygen, and sulfur.
• the heteroaryl ring may be fused or otherwise attached to one or more heteroaryl rings, aromatic or nonaromatic hydrocarbon rings or heterocycloalkyl rings. Examples of heteroaryl groups include pyridyl, furyl, and thienyl.“Heteroarylene” means a divalent heteroaryl group.
• Alkoxy refers to an alkyl group attached to the parent molecular moiety through an oxygen bridge. Examples of alkoxy groups include, for instance, methoxy, ethoxy, propoxy and isopropoxy.“Thioalkyl” means an alkyl group attached to the parent molecule through a sulfur bridge. Examples of thioalkyl groups include, for instance, methylthio, ethylthio, n-propylthio and iso-propylthio. “Aryloxy” refers to an aryl group attached to a parent molecular moiety through an oxygen bridge. Examples include phenoxy. “Arylthio” refers to an aryl group attached to a parent molecular moiety through a sulfur bridge. Examples include phenylthiol. “Cyclic alkoxy” means a cycloalkyl group attached to the parent moiety through an oxygen bridge.
• Alkylamine refers to an alkyl group attached to the parent molecular moiety through an -NH bridge.
• Alkyleneamine means a divalent alkylamine group, such as -CH2CH2NH-.
• the silicone-containing component may comprise one or more
• a C6-C14 aryl group optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof, e. halo, f. alkoxy, cyclic alkoxy, or aryloxy, g. siloxy, h.
• Alkyleneoxy refers to groups of the general formula -(alkylene-0) p - or -(O-alkylene) p -, wherein alkylene is as defined above, andp is from 1 to 200, or from 1 to 100, or from 1 to 50, or from 1 to 25, or from 1 to 20, or from 1 to 10, wherein 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. If p is greater than 1 , then each alkylene may be the same or different and the alkyleneoxy may be in block or random configuration.
• the reactive monomer mixture includes at least one polyamide.
• polyamide refers to polymers and copolymers comprising repeating units containing amide groups.
• the polyamide may comprise cyclic amide groups, acyclic amide groups and combinations thereof, and may be any polyamide known to those of skill in the art.
• Acyclic polyamides comprise pendant acyclic amide groups and are capable of association with hydroxyl groups.
• Cyclic polyamides comprise cyclic amide groups and are capable of association with hydroxyl groups.
• Polyamides suitable for use with the presently disclosed compositions and methods are disclosed in U.S. Patent Application Publication No.
• c is the speed of light in a vacuum and v is the phase velocity of light in the medium.
• composition (C) (i) at least one hydrophobic monomer; (ii) at least one hydroxyl-containing monomer; (iii) at least one crosslinking agent; and (iv) at least one polyamide, wherein the reactive monomer mixture comprises the polyamide in an amount of about 0.10 to about 5.0 weight percent (hereinafter“Composition (C)”).
• the at least one bis(2-hydroxypropyl (meth)acrylate) terminated polysiloxane crosslinking agent is a bis(2-hydroxypropyl (meth)acrylate) terminated poly(dimethylsiloxane).
• Composition (A) further comprises at least one hydrophilic monomer.
• the at least one hydrophilic monomer is selected from vinyl pyrrolidone, N-vinyl-N-methyl acetamide, N-methyl methacrylamide, N-vinyl acetamide, N,N- dimethylacrylamide, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) methacrylate, or any combination thereof.
• Composition (A) further comprises at least one UV absorbing compound in the reactive monomer mixture.
• the UV absorbing compound may take the form of Formula I:
• X is O, S, NR, SO, or S0 2 ;
• Y is a linking group;
• P g is a polymerizable group
• R at each occurrence is independently H, Ci-Ce alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or Y-P g ;
• Compounds of Formula I preferably contain one or two Y-P g groups. More preferably, the compounds contain one Y-P g group.
• the at least one UV absorbing compound comprises 2-(2'- hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 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-(l 0-methylacridin-9(l OH)-ylidene)acetamido)ethyl methacrylate or any combinations thereof.
• the at least one UV absorbing compound is 2- (2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate.
• (meth)acrylate also known as ethylene glycol dicyclopentenyl ether (meth)acrylate
• methacrylate also known as ethylene glycol dicyclopentenyl ether (meth)acrylate
• Composition (A) has a refractive index of at least 1.45 and an Abbe number of at least 45. In other embodiments, Composition (A) has a refractive index of at least 1.48 and an Abbe number of at least 50. In yet other embodiments, Composition (A) has a refractive index of at least 1.50 and an Abbe number of at least 50.
• the reactive monomer mixture comprises the at least one aromatic (meth)acrylate in an amount between about 40 and about 80 weight percent, including about 40, 45, 50, 55, 60, 65, 70, 75, and 80 weight percent. In certain embodiments, the reactive monomer mixture comprises the at least one aromatic (meth)acrylate in an amount between about 60 and about 75 weight percent, including about 60, 65, 70, and 75 weight percent. In some embodiments,
• the weight percent of the at least one aromatic (meth)acrylate present in the reactive monomer mixture is calculated excluding a diluent.
• the crosslinking agent is a bis(2-hydroxypropyl (meth)acrylate) terminated poly(dimethylsiloxane).
• the at least one bis(2- hydroxypropyl (meth)acrylate) terminated polysiloxane crosslinking agent has formula:
• n is an integer from 5 to 50, including 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45,
• (meth)acrylate is n-hexyl acrylate.
• the aryl group is a phenyl group.
• the aryl group is present in the aromatic (meth)acrylate as part of an ary lalkyl group (e.g., benzyl, 2-phenylethyl, 3-phenylpropyl, or 4-phenylbutyl), an aryloxyalkyl group (e.g., phenoxymethyl, 2-phenoxyethyl, 3 -phenoxypropyl, or 4- phenoxy butyl), or an arylthioalkyl group (e.g., phenylthiomethyl, 2-phenylthioethyl, 3- phenylthiopropyl, or 4-phenylthiobutyl).
• the aromatic (meth)acrylate is selected from the group consisting of 2-phenylethyl (meth)acrylate, 2-phenoxyethyl
• the hydrophobic (meth)acrylate is a cycloaliphatic (meth)acrylate.
• the cycloaliphatic group has one cycloaliphatic ring.
• the cycloaliphatic ring may be a C3-C8 cycloalkyl group, a C3-C7 cycloalkyl group, a C4-C7 cycloalkyl group, or a C5-C6 cycloalkyl group.
• the at least one cycloaliphatic (meth)acrylate has at least one cycloaliphatic group comprising at least one carbon-carbon double bond.
• the cycloaliphatic (meth)acrylate comprises cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 2-cyclohexylethyl (meth)acrylate, 3 - cyclohexylpropyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate,
• Composition (C) further comprises at least one hydrophilic monomer.
• the at least one hydrophilic monomer is selected from vinyl pyrrolidone, N-vinyl -N-methyl acetamide, N-methyl methacrylamide, N-vinyl acetamide, N,N- dimethylacrylamide, hydroxyethyl acrylamide, N-(2-hydroxypropyl)acrylamide, N-(3- hydroxypropyl)acrylamide, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) methacrylate, or any combination thereof.
• composition (C) has a refractive index of at least 1.45 and an Abbe number of at least45; in other embodiments, the composition has a refractive index of at least 1.48 and an Abbe number of at least 50; or, in yet other embodiments, the composition has a refractive index of at least 1.50 and an Abbe number of at least 50.
• the presently disclosed subject matter provides a device comprising a Composition (A, B or C) as described immediately hereinabove.
• the ophthalmic device is an intraocular implant or lens. More specifically, the presently disclosed subject matter also provides intraocular implants and/or lenses made at least partially or completely from the compositions (A-C) described herein. Such intraocular implants or lenses can include an optic portion and one or more haptic portions. Typically, the compositions of the presently disclosed subject matter will make up part or all of the optic portion of the intraocular implant or lens. In some embodiments, the optic portion of the implant or lens will have a core made from one of the compositions described herein surrounded by different polymer or material. Implants or lenses in which the optic portion is made up of at least partially of one of the compositions of the presently disclosed subject matter will usually also have a haptic portion. The haptic portion can also be made of polymer of the disclosure or can be made of a different material, for example another polymer.
• the intraocular implant or lens of the presently disclosed subject matter is a one-piece lens having a soft, foldable central optic region and an outer peripheral region (haptic-region) in which both regions are made of the same polymer.
• FC front curve plastic mold
• PEA 2-phenylethyl acrylate [CAS 3530-36-7] (Melrob, Parmon)
• EGDMA ethylene glycol dimethacrylate (Esstech)
• PVMA 570kDa polyvinylmethyacetamide. PVMA was prepared as follows:
• Clause 10 The composition of clause 9, wherein the crosslinking agent is a bis(2- hydroxypropyl (meth)acrylate) terminated poly(dimethylsiloxane).
• Clause 18 The composition of clause 16 or clause 17, wherein the reactive monomer mixture comprises the UV absorbing compound in an amount between about 0.1 and about 5 weight percent, between about 1 and about 4 weight percent, or between about 1 and about 3 weight percent.
• Clause 19 The composition of any one of clauses 1 -18, further comprising an unsaturated monomer having a polymerizable group and at least one other carbon-carbon double bond.
• Clause 22 The composition any one of clauses 19-21 , wherein the unsaturated monomer is selected from cyclohexenyl ether acrylate, N,N-diallyl acrylamide, diallyl maleate, allyl (meth)acrylate, 2-(allyloxy)ethyl (meth)acrylate, ((lR,2S,4R)-bicyclo[2.2.1]hept-5-en-2- yl)methyl (meth)acrylate, ethylene glycol dicyclopentenyl ether (meth)acrylate, and any combination thereof.
• Clause 23 The composition of any one of clauses 1 -22, further comprising at least one diluent in the reactive monomer mixture.
• Clause 27 An ophthalmic device comprising the composition of any one of clauses 1 -26.
• n is an integer from 5 to 50.
• Clause 55 The composition of any one of clauses 37-54, wherein the reactive monomer mixture comprises the crosslinking agent in an amount of about 18% by weight.
• Clause 57 The composition of clause 56, wherein the polyamide is selected from poly(vinyl pyrrolidone), poly(N-vinyl-N-methyl acetamide), poly(N-vinyl acetamide), poly(dimethyl acrylamide), and a copolymer or a mixture thereof.
• Clause 64 The composition of any one of clauses 37-63, further comprising at least one diluent in the reactive monomer mixture.
• Clause 67 The composition of any one of clauses 37-66, wherein the free radical polymerization is a photopolymerization using a bisacylphosphine oxide initiator.
• Clause 70 A method for making an ophthalmic device, the method comprising:
• Clause 76 The method of any one of clauses 70-75, further comprising an irradiation step using a femtosecond two photon laser.
• Clause 77 The method of any of clauses 70-76, further comprising a step of sterilizing ihe ophthalmic device.
• a composition made by free radical polymerization of a reactive monomer mixture comprising:
• Clause 79 The composition of clause 78, wherein the hydrophobic monomer is a hydrophobic (meth)acrylate monomer.
• Clause 84 The composition of clause 83, wherein the C1-C18 alkyl (meth)acrylate is n- hexyl acrylate.
• Clause 87 The composition of clause 86, wherein the aromatic (meth)acrylate is 2- phenylethyl acrylate.
• Clause 90 The composition of clause 80, wherein the hydrophobic (meth)acrylate is a cycloaliphatic (meth)acrylate.
• cycloaliphatic (meth)acrylate comprises cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 2-cyclohexylethyl (meth)acrylate, 3-cyclohexylpropyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, (( 1 R,2S,4R)-bicyclo[2.2. l]hept-5-en-2-yl)methyl (meth)acrylate, ethylene glycol dicyclopentenyl ether (meth)acrylate, or any combination thereof.
• Clause 95 The composition of any one of clauses 78-94, wherein the reactive monomer mixture comprises the hydrophobic monomer in an amount between about 50 and 90 weight percent.
• Clause 96 The composition of any one of clauses 78-95, wherein the hydroxyl-containing monomer is a hydroxyalkyl (meth)acrylate.
• Clause 103 The composition of any one of clauses 78-102, wherein the crosslinking agent is selected from the group consisting of a non-cycloaliphatic crosslinking agent, a cycloaliphatic crosslinking agent, and any combination thereof.
• Clause 1 1 1. The composition of clause 1 10, wherein n is 20.
• Clause 1 18. The composition of any one of clauses 78-1 17, wherein the reactive monomer mixture comprises the polyamide in an amount between about 0.1 weight percent and about 3 weight percent.
• UV absorbing compound in the reactive monomer mixture UV absorbing compound in the reactive monomer mixture.
• Clause 121 The composition of clause 120, wherein the UV absorbing compound is a compound of Formula I, 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 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-(l 0-methylacridin-9(l OH)- ylidene)acetamido)ethyl methacrylate, or any combination thereof.
• the UV absorbing compound is a compound of Formula I, 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 2-(2- cyano-2-(9H-thioxanthen-9-ylidene)acetamid
• Clause 132 A method for making an ophthalmic device, the method comprising either: d. preparing a blank from the composition of any of clauses 78-126 and machining an ophthalmic device from the blank; e. molding an ophthalmic device from the composition of any of clauses 78-126; or f. molding an ophthalmic device from the composition of any of clauses 78-126 and machining the surface of the ophthalmic device.
• Clause 135. The method of any one of clauses 129-134, further comprising an irradiation step using a femtosecond two photon laser.

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