Ophthalmic lens material comprising fluoro group

Abstract

This invention generally relates to an ophthalmic lens comprising a polymer obtainable from a polymerizable composition. The invention also provides a polymerizable composition, and methods for preparing lenses from the polymerizable composition. The ophthalmic lens comprises a polymer obtained from curing a polymerizable composition comprising: a first polymerizable monomer having an alkenyl group and at least one fluoro group; and a second polymerizable component selected from a polymerizable monomer having an alkenyl group and at least one siloxane group, and a polymerizable pre-polymer having an alkenyl group and at least one siloxane group.

Description

[0001] OPHTHALMIC LENS

[0002] Related Applications

[0003] The present application is related to, and claims priority to and the benefit of GB 2311530.6 filed on 27 July 2023 (27.07.2023), the contents of which are incorporated by reference in their entirety.

[0004] Technical Field

[0005] This invention generally relates to an ophthalmic lens comprising a polymer obtainable from a polymerizable composition. The invention also provides a polymerizable composition, and methods for preparing lenses from the polymerizable composition.

[0006] Background

[0007] Ophthalmic lenses are devices for correcting defective vision, and include contact and intraocular lenses. In particular, it has become commonplace to use a contact lens for correction of visual defects. Additionally, it has become commonplace to replace cataractous lens with an intraocular lens (lOLs) using surgical procedures. lOLs include phakic, aphakic and pseudo-phakic intraocular lenses.

[0008] Ophthalmic lenses are often manufactured from poly and perfluoro alkyl substances (PFAS). PFAS typically encompasses fluorinated substances that contain at least one fully fluorinated methyl or methylene atoms (without any H / CI / Br / l atom attached to it). Any compound with at least a perfluorinated methyl group (-CH3) or a perfluorinated methylene group (-CF2-) is also normally classified as a PFAS.

[0009] PFAS tend to be repellent to both water and oily substances, are chemically inert, even to acids and alkalis, and remain stable at high temperatures. Thus, PFAS are useful in the manufacture of polymeric materials.

[0010] Polymers including PFAS components can provide useful qualities to ophthalmic lenses. Various PFAS monomers are currently used in rigid contact lens polymers and intraocular lens polymers, such as hexafluoroisopropyl methacrylate (HFPM, CAS 3063-94-3), trifluoroethyl methacrylate (CAS 352-87-4) and bis-hexafluoroisopropyl itaconate (CAS 98452-82-5). The PFAS monomers help to improve the oxygen permeabilities of such materials, which is particularly important for rigid contact lenses. Using non-PFAS monomers leads to a performance drop in the lens materials, notably a reduction in oxygen permeability as well as poorer deposit resistance, physical performance and optical quality.

[0011] Certain PFAS are harmful to the environment. PFAS tend to be persistent in the environment or may convert in the environment to a different PFAS substance which is persistent (such as trifluoroacetic acid (TFA)). The PFAS compounds may bioaccumulate and become toxic. As a result, there is growing regulation around certain PFAS substances. For example, in 2021 , five member states of the European Union (Germany, Denmark, Netherlands, Norway and Sweden) submitted a notification of intention to ban the use of PFAS compounds to the European Chemicals Agency (ECHA).

[0012] There is therefore a need to provide new polymers, which are suitable for ophthalmic lenses, which provide the same advantageous properties of PFAS monomers but without the negative environmental impact.

[0013] Summary of the Invention

[0014] In general, the present invention provides an ophthalmic lens comprising a polymer obtained from a polymerizable composition. The present inventors have surprisingly found that using a polymerizable composition including the combination of a siloxane containing monomer or prepolymer along with a fluoro containing monomer results in a lens having excellent optical properties, such as increased refractive index, and good physical characteristics, such as oxygen permeability, hardness, good lipid deposit resistance, and strength.

[0015] Such properties have previously been achieved using a PFAS containing polymer.

[0016] However, the present inventors have surprisingly found that by using the siloxane containing component according to the present invention, this allows for the use of a fluoro containing monomer which would normally be expected to produce inferior lens materials, such as non- PFAS monomers.

[0017] For example, the inventors have discovered that fluoro containing monomers including those which do not contain a trifluoromethyl group connected to a carbon atom, preferably do not contain a trifluoromethyl group; and / or do not contain two or more adjacent diflouromethylene groups, preferably do not contain a difluoromethylene group, may be used in the invention, These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS) as they are less persistent and so less harmful to the environment, but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0018] The inventors have also found that a siloxane containing monomer or prepolymer provides beneficial properties to PFAS containing polymers (i.e. including a fully fluorinated methyl or methylene atom). It is noted that certain PFAS do not have the negative environmental effects often associated with PFAS, and so improvements to polymer products, such as ophthalmic lenses, including these certain PFAS is still important and advantageous.

[0019] Without wishing to be bound by theory, permeability is dependent on the solubility (k) of the gas and its diffusion rate (D) through the material. The siloxane containing component has relatively low intermolecular forces and relatively unhindered single bonds that link the silicon and oxygen, providing a higher free volume and higher degree of chain mobility. Its low polarity provides good solubility for non-polar oxygen.

[0020] It is advantageous to combine fluorine and siloxane containing components. High oxygen permeability can be achieved by adding a silicone component to a material in the absence of a fluorinated species, but such materials are typically soft, lack dimensional stability (change shape over time) and have poor deposit resistance (components from the tears foul the lens surfaces). By combining fluorine and a siloxane containing component as in the present invention, these properties can be improved while maintaining oxygen permeability.

[0021] Accordingly, in a first aspect of the invention there is provided an ophthalmic lens comprising a polymer obtained from curing a polymerizable composition comprising: a first polymerizable monomer having an alkenyl group and at least one fluoro group; and a second polymerizable component selected from a polymerizable monomer having an alkenyl group and at least one siloxane group, and a polymerizable pre-polymer having an alkenyl group and at least one siloxane group.

[0022] In a first embodiment, the second polymerizable component is the polymerizable monomer having an alkenyl group and at least one siloxane group.

[0023] In a second embodiment, the second polymerizable component is the polymerizable prepolymer having an alkenyl group and at least one siloxane group.

[0024] The present inventors have established that this polymerizable composition provides a polymer that has suitable oxygen permeability, wettability, hardness and dimensional stability, for use in an ophthalmic lens. The ophthalmic lens may be an intraocular lens or a contact lens. Preferably, the ophthalmic lens is a contact lens.

[0025] In a second aspect of the invention there is provided a polymerizable composition for obtaining a polymer for use in the ophthalmic lens of the first aspect of the invention comprising: a first polymerizable monomer having an alkenyl group and at least one fluoro group; and a second polymerizable component selected from a polymerizable monomer having an alkenyl group and at least one siloxane group, and a polymerizable pre-polymer having an alkenyl group and at least one siloxane group.

[0026] In some embodiments the first polymerizable monomer comprises: a) an (alkyl)acrylate group comprising the alkenyl group, wherein the one or more fluoro groups are provided within a moiety connected to the alcoholic portion of the (alkyl)acrylate group; or b) a substituted aryl group connected directly to the alkenyl group, wherein the aryl group is substituted with the one or more fluoro groups.

[0027] In some embodiments, the first polymerizable monomer does not contain a trifluoromethyl group connected to a carbon atom, preferably the first polymerizable monomer does not contain a trifluoromethyl group; and / or the first polymerizable monomer does not contain two or more adjacent diflouromethylene groups, preferably the first polymerizable monomer does not contain a difluoromethylene group.

[0028] These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS), but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0029] In some embodiments, the first polymerizable monomer is of the general formula (I): wherein: -R1, -R2and -R3are each independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R1is methyl, -R2is -H, and R3is -H;

[0030] -L1- is selected from a covalent bond, where the asterisk * indicates the point of connection to -R4;

[0031] -R4is selected from substituted C6-12 aryl, substituted C1-10 alkyl and substituted C2-C10 heteroalkyl, and the aryl, alkyl and heteroalkyl groups are substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and are optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo; and where -R4is substituted C6-12 aryl then -R5- is C1-10 alkylene or C2-C10 heteroalkylene, and where -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl then -R5- is a covalent bond.

[0032] When the first polymerizable monomer has the general formula (I), this provides the ophthalmic lens with improved oxygen permeability.

[0033] In preferred embodiments, the first polymerizable monomer has the general formula (I): i1R1r4RS YJLR2wherein:

[0034] -R1, -R2and -R3are each independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R1is methyl, -R2is -H, and R3is -H;

[0035] -L1- is selected from a covalent bond, where the asterisk * indicates the point of connection to -R4;

[0036] -R4is selected from substituted C6-12 aryl and substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, the aryl group is substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and the alkyl and heteroalkyl groups are substituted with at least one fluoro substituent or at least one group containing a fluoro substituent wherein the at least one fluoro substituent or at least one group containing a fluoro substituent are selected from one or more of the following: -F, -CF3, -CFH2, -CF2H, -CF2CI, -CFCI2, and mixtures thereof, and where -R4is -CF3then -L1- is where the asterisk * indicates the point of connection to -R4, and the aryl, alkyl and heteroalkyl groups are optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo; and where -R4is substituted C6-12 aryl then -R5- is C1-10 alkylene or C2-C10 heteroalkylene, and where -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl then -R5- is a covalent bond.

[0037] In some embodiments, the fluoro substituents are selected from one or more of the following: -F, -CF3, -CF2H, -CF2CI, -CFCI2, and mixtures thereof.

[0038] These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS), but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0039] In some such embodiments, the second polymerizable component having an alkenyl group and at least one siloxane group has the general formula (II): wherein:

[0040] -R6, -R7, and -R8are independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R6is methyl, -R7is -H, and -R8is -H; -L2- is selected from a covalent bond, wherein the asterisk * indicates the point of connection to -R9-;

[0041] -R9- is selected from optionally substituted Ce-io arylene, optionally substituted C1-10 alkylene and optionally substituted C2-10 heteroalkylene; where -R9- is optionally substituted Ce-io arylene then -R11- is optionally substituted C1-10 alkylene, optionally substituted C2-10 heteroalkylene, or a covalent bond, and where -R9- is optionally substituted C1-10 alkylene or optionally substituted C2-10 heteroalkylene then -R11- is a covalent bond; and

[0042] -R10is -Si(OSI(R12)3)3 -Si(OSi(R12)3)2Ri2, -Si(O[Si(R12)2O]rRi2)2R12, or -Si(O[SI(R12)2O]rRi2)3 where each -R12is independently selected from C1-10 alkyl and -OH, and r is 2 to 25.

[0043] In some embodiments, -R9- is arylene, such as phenylene, such as phenyl-1 , 4-ene. When, -R9- is arylene, this provides advantages over other siloxane containing component, as the molecule is more rigid. This rigidity is thought to allow greater oxygen permeability to be achieved without the materials becoming soft / flexible.

[0044] In a first embodiment, the second polymerizable component is the polymerizable monomer having an alkenyl group and at least one siloxane group. In such embodiments, -R10may be -Si(OSi(R12)3)3 or -Si(OSi(R12)3)2Ri2.

[0045] In a second embodiment, the second polymerizable component is the polymerizable prepolymer having an alkenyl group and at least one siloxane group. In such embodiments, -R10may be -Si(O[Si(R12)2O]rRi2)2R12, or -SI(O[Si(R12)2O]rRi2)3.

[0046] In the first embodiment and the second embodiment, use of the polymerizable monomer or prepolymer including at least one siloxane group as the second polymerizable component is thought to provide the ophthalmic lens with improved oxygen permeability. Without wishing to be bound by theory, it is thought that the siloxane interacts with the fluorine containing monomer, to produce a synergistic improvement to the resulting polymer’s properties, in particular the oxygen permeability.

[0047] Thus, when the first and second polymerizable components are taken together, these act to modifies oxygen permeability within rigid contact lens polymers. This allows the ophthalmic lenses made using alternative fluorine containing non-PFAS monomers to achieve excellent oxygen permeabilities. The second polymerizable components may additionally improve the oxygen permeabilities of ophthalmic lenses made using conventional PFAS monomers.

[0048] In a third aspect, there is provided an optical material comprising a polymer obtained or obtainable from curing a polymerizable composition of the second aspect.

[0049] In a fourth aspect, there is provided a method of forming an optical material, comprising curing a polymerizable composition of the second aspect, and optionally annealing the resulting cured material.

[0050] In a fifth aspect, there is provided a method of forming an ophthalmic lens, wherein the method comprises the steps of: i) curing the polymerizable composition of the second aspect in a mould to form a molded product; ii) optionally annealing the moulded product; and iii) working the molded product to form an ophthalmic lens.

[0051] In some embodiments, the molded product is a polymer rod. In some embodiments, the working step comprises lathing the polymer rod. Preferably, the polymer rod is lathed to form polymer buttons. The polymer buttons may then be further shaped (e.g., machined, polished) to form an ophthalmic lens.

[0052] In such embodiments, the method may comprise the steps of: i) curing the polymerizable composition of the second aspect in a substantially rod-shaped mould to form a polymer rod; ii) optionally annealing the polymer rod; and iii) working the polymer rod to form an ophthalmic lens.

[0053] In some embodiments, the method is a method of forming an ophthalmic lens of the first aspect.

[0054] In other aspects there is provided a lens blank for an ophthalmic lens obtained or obtainable from the resin of the third aspect of the invention.

[0055] Other aspects and embodiments of the invention are as described below. Detailed Description of the Invention

[0056] The present invention generally provides an ophthalmic lens comprising a polymer obtained from a polymerizable composition as described herein. The ophthalmic lens of the invention has good optical properties, such as increased refractive index, and / or improved physical characteristics, such as improved oxygen permeability, while being formed from biocompatible, and preferably being formed from non-PFAS, substances.

[0057] Some polymers which include fluorine containing monomers and siloxane containing components are known. However, these known polymers differ from the present invention.

[0058] For example, EP0277771 describes contact lenses formed from the polymerization product of: (a) at least one fluroorgano monomer; (b) at least one siloxyl alkyl ester; and a member of the group consisting of: (i) at least one poly(organosiloxane) monomer, and (ii) mixtures of said poly(organosiloxane) monomer. Also described are contact lenses prepared from 60-65 wt% hexafluoroisopropyl methacrylate and 25-30 wt% TRIS.

[0059] EP1750157 describes contact lenses prepared from 54 wt% hexafluoroisopropyl methacrylate and 46 wt% styryl TRIS, and 35 wt% trifluoroethyl methacrylate and 55 wt% styryl TRIS, respectively.

[0060] US6286955 describes contact lenses prepared from 20 wt% hexafluoroisopropyl methacrylate and 45 wt% TRIS.

[0061] US5002979 describes contact lenses prepared from 75 wt% hexafluoroisopropyl methacrylate and 19 wt% TRIS, 65-85 wt% trifluoroethyl methacrylate and 9.5-29 wt% TRIS, and 75 wt% hexafluorobutyl methacrylate and 19 wt% TRIS, respectively.

[0062] In each of these documents the flurorine containing monomers are PFAS monomers. However, the present inventors have surprisingly found that by using the siloxane containing component according to the present invention, this allows for the use of non-PFAS fluoro containing monomer which would normally be expected to produce inferior lens materials.

[0063] The present inventors have found that ophthalmic lenses having improved properties can be obtained from a polymer obtainable from curing a polymerizable composition comprising: a first polymerizable monomer having an alkenyl group and at least one fluoro group; and a second polymerizable component selected from a polymerizable monomer or pre-polymer having an alkenyl group and at least one siloxane group. The invention provides advantageous properties for ophthalmic lenses using PFAS monomers and enhances the properties of fluorine containing non-PFAS monomers in ophthalmic lenses, as described herein.

[0064] Polymerizable Composition

[0065] The invention provides a polymerizable composition for preparing a resin for an ophthalmic lens.

[0066] The polymerizable composition comprises: a first polymerizable monomer having an alkenyl group and at least one fluoro group; and a second polymerizable component selected from a polymerizable monomer having an alkenyl group and at least one siloxane group, and a polymerizable pre-polymer having an alkenyl group and at least one siloxane group.

[0067] The present inventors have established that polymer ophthalmic lenses, particularly contact lenses, formed from such a composition may have good oxygen permeability, wettability, deposit resistance, hardness and dimensional stability.

[0068] In the present invention, the first polymerizable monomer has at least one fluoro group. The at least one fluoro group may provide the ophthalmic lens with chemical inertness, increased oxygen permeability, deposit resistance, biocompatibility, comfort, wettability, rigidity, lathability, durability, scratch resistance and dimensional stability.

[0069] The first polymerizable monomer may comprise at least two or more fluorine atoms.

[0070] The first polymerizable monomer may comprise at least three or more fluorine atoms.

[0071] The first polymerizable monomer may comprise at least four or more fluorine atoms.

[0072] In some embodiments, the first polymerizable monomer comprises: a) an (alkyl)acrylate group comprising the alkenyl group, wherein the one or more fluoro groups are provided within a moiety connected to the alcoholic portion of the (alkyl)acrylate group; or b) a substituted aryl group connected directly to the alkenyl group, wherein the aryl group is substituted with the one or more fluoro groups.

[0073] In some embodiments, the first polymerizable monomer comprises an (alkyl)acrylate group comprising the alkenyl group, and the one or more fluoro groups are provided within a moiety connected to the alcoholic portion of the acrylate group. In some embodiments, the (alkyl)acrylate group comprising the alkenyl group comprises at least one terminating group selected from:-CFH2, -CF2H, -CFCI2and -CF2CI.

[0074] In some embodiments, the one or more fluoro group of the (alkyl)acrylate group comprising the alkenyl group each contain of one or two fluorine atoms, respectively.

[0075] The first polymerizable monomer may further comprise a substituted aryl group connected to the alcoholic portion of the acrylate group, and the aryl group is substituted with the one or more fluoro groups.

[0076] The substituted aryl group may be connected directly to the alcoholic oxygen atom of the (alkyl)acrylate group. The substituted aryl group may be spaced at least one atom away from the alcoholic oxygen atom of the (alkyl)acrylate group.

[0077] The substituted aryl group may be substituted phenyl, wherein the substituted phenyl group is substituted with one or more fluoro groups.

[0078] The substituted aryl group may be selected from mono-, di-, tri-, tetra-, and penta-fluorophenyl.

[0079] In preferred embodiments, the substituted aryl group is pentafluorophenyl.

[0080] In other embodiments, the first polymerizable monomer comprises a substituted aryl group connected directly to the alkenyl group, and the aryl group is substituted with the one or more fluoro groups.

[0081] The substituted aryl group may be substituted phenyl, wherein the substituted phenyl group is substituted with one or more fluoro groups.

[0082] The substituted aryl group may be selected from mono-, di-, tri-, tetra-, and penta-fluorophenyl.

[0083] In preferred embodiments, the substituted aryl group is pentafluorophenyl.

[0084] In some embodiments, the first polymerizable monomer does not contain a trifluoromethyl group connected to a carbon atom, preferably the first polymerizable monomer does not contain a trifluoromethyl group; and / or the first polymerizable monomer does not contain two or more adjacent diflouromethylene groups, preferably the first polymerizable monomer does not contain a difluoromethylene group. In some embodiments, the first polymerizable monomer does not contain a trifluoromethyl group connected to a carbon atom, preferably the first polymerizable monomer does not contain a trifluoromethyl group.

[0085] In some embodiments, the first polymerizable monomer does not contain two or more adjacent diflouromethylene groups, preferably the first polymerizable monomer does not contain a difluoromethylene group.

[0086] In some embodiments, the first polymerizable monomer does not contain a trifluoromethyl group connected to a carbon atom, preferably the first polymerizable monomer does not contain a trifluoromethyl group; and the first polymerizable monomer does not contain two or more adjacent diflouromethylene groups, preferably the first polymerizable monomer does not contain a difluoromethylene group.

[0087] These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS), but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0088] In preferred embodiments, the first polymerizable monomer has the general formula (I): wherein:

[0089] -R1, -R2and -R3are each independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R1is methyl, -R2is -H, and R3is -H;

[0090] -L1- is selected from a covalent bond, where the asterisk * indicates the point of connection to -R4;

[0091] -R4is selected from substituted C6-12 aryl and substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, and the aryl, alkyl and heteroalkyl groups are substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo; and where -R4is substituted C6-12 aryl then -R5- is C1-10 alkylene or C2-C10 heteroalkylene, and where -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl then -R5- is a covalent bond.

[0092] The heteroalkyl and heterolakylene may contain one or more heteroatoms selected from O, N and S.

[0093] In some embodiments, where -R5- is C1-10 alkylene or C2-C10 heteroalkylene, the alkylene or heteroalkylene may include at least one fluoro substituent bonded to a carbon atom. Preferably, where R5- is C1-10 alkylene or C2-C10 heteroalkylene, the alkylene or heteroalkylene are nonsubstituted.

[0094] The heteroatom(s) of the heteroalkyl and heterolakylene is typically spaced at least one carbon atom away from the alcoholic oxygen atom of -L1- when -L1- is

[0095] The heteroatom(s) of the heteroalkyl and heterolakylene is not a terminal atom. In other words, the heteroatom(s) are connected to at least two non-hydrogen atoms.

[0096] The heteroalkyl and heterolakylene may comprise an ether, secondary amine, or thioether group.

[0097] In some embodiments, -R1, -R2, and -R3are all -H. In some embodiments, -R1, -R2and -R3are all C1-4 alkyl. In some embodiments, -R1, -R2, and -R3are all methyl.

[0098] In some embodiments, -R1is C1-4 alkyl, -R2is -H, and -R3is -H. In some embodiments, -R1is -H, -R2is C1-4 alkyl, and -R3is -H.

[0099] In some embodiments, -R1is methyl, -R2is -H, and -R3is H. In some embodiments, -R1is -H, - R2is methyl, and -R3is H.

[0100] In some embodiments, -L1- is a covalent bond. In some embodiments, -L1- is the asterisk * indicates the point of connection to -R4.

[0101] In some embodiments, -L1- is , where the asterisk * indicates the point of connection to -R4.

[0102] In some embodiments, -L1- is where the asterisk * indicates the point of connection to -R4.

[0103] In some embodiments, -L1- is , where the asterisk * indicates the point of connection to -R4.

[0104] In some embodiments, -R4is selected from substituted C6-12 aryl, substituted C1-10 alkyl and substituted C2-C10 heteroalkyl, and the aryl, alkyl and heteroalkyl groups are substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent.

[0105] -R4may be optionally further substituted with one or more of the following: halo substituents selected from chloro, iodo and bromo, groups containing halo substituents selected from chloro, iodo and bromo, hydroxyl groups, amino groups, and combinations thereof.

[0106] In some embodiments, -R4is optionally further substituted with one or more chloro substituents, or one or more groups containing chloro substituents.

[0107] In some embodiments, -R4is substituted C6-12 aryl, and the aryl group is substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halos substituents selected from chloro, iodo and bromo, and -R5- is C1-10 alkylene or C2-C10 heteroalkylene.

[0108] In some embodiments, -R4is selected from substituted phenyl, substituted naphthyl, and substituted phenylbenzene, wherein the phenyl, naphthyl and phenylbenzene are substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo, and -R5- is C1-10 alkylene or C2-C10 heteroalkylene.

[0109] In some embodiments, -R4is phenyl substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo, and -R5- is C1-10 alkylene or C2-C10 heteroalkylene.

[0110] In some embodiments, -R4is selected from mono-, di-, tri-, tetra-, and penta-fluorophenyl, and -R5- is C1-10 alkylene or C2-C10 heteroalkylene.

[0111] In preferred embodiments, -R4is pentafluorophenyl, and -R5- is C1-10 alkylene or C2 C10 heteroalkylene.

[0112] Where R4is as described above, -R5- is C1-10 alkylene, preferably C1-4 alkylene, preferably methylene. In other embodiments, -R5- is C2-C10 heteroalkylene, preferably C2-C6 heteroalkylene.

[0113] In some embodiments, -R4is substituted Ce-io aryl, and the aryl group is substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halos substituents selected from chloro, iodo and bromo, and -R5- is C1-10 alkylene. In such embodiments, -R5- may be C1-4 alkylene, preferably methylene.

[0114] In some embodiments, -R4is substituted aryl, and the aryl group is substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halos substituents selected from chloro, iodo and bromo, and -R5- is C2-C10 heteroalkylene. In such embodiments, -R5- may be C2-C6 heteroalkylene.

[0115] In preferred embodiments, -R4is pentafluorophenyl, and -R5- is C1-10 alkylene or C2-C10 heteroalkylene.

[0116] In some embodiments, -R4is pentafluorophenyl, and -R5- is C1-10 alkylene.

[0117] In some embodiments, -R4is pentafluorophenyl, and -R5- is C1-4 alkylene.

[0118] In preferred embodiments, -R4is pentafluorophenyl, and -R5- is methylene.

[0119] In some embodiments, -R4is pentafluorophenyl, and -R5- is C2-C10 heteroalkylene.

[0120] In some embodiments, -R4is pentafluorophenyl, and -R5- is C2-C6 heteroalkylene.

[0121] In other embodiments, -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent and is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halos substituents selected from chloro, iodo and bromo, and -R5- is a covalent bond.

[0122] In some embodiments, -R4is substituted C1-10 alkyl, such as C1-4 alkyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent and is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halos substituents selected from chloro, iodo and bromo, and - R5- is a covalent bond.

[0123] In some embodiments, -R4is substituted C2-C10 heteroalkyl, such as C2-C6 heteroalkyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent and is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halos substituents selected from chloro, iodo and bromo, and -R5- is a covalent bond.

[0124] In some embodiments, the substituted C1-10 alkyl or substituted C2-C10 heteroalkyl comprises at least one terminating group selected from: -CFH2, -CF2H, -CFCI2 and -CF2CI.

[0125] In some embodiments, the at least one group containing a fluoro substituent each contain one or two fluorine atoms, respectively. In some embodiments, -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, substituted with the at least one fluoro substituent, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of the following: -F, -CF3, -CFH2, -CF2H, -CF2CI, -CFCI2, and mixtures thereof, wherein -R4is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CC , -CCI2H, -CBr3, -CBr2H, -Cl3, -CI2H, and mixtures thereof, and -R5- is a covalent bond.

[0126] In some embodiments, -R4is substituted C1-10 alkyl or substituted C2.Cio heteroalkyl, substituted with the at least one fluoro substituent, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of the following: -F, -CF3, -CF2H, -CF2CI, -CFCI2, and mixtures thereof, wherein -R4is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CCI3, -CCI2H, -CBr3, -CBr2H, -Cl3, -CI2H, and mixtures thereof, and -R5- is a covalent bond.

[0127] In some embodiments, -R4is substituted C1-10 alkyl or substituted C2.Cio heteroalkyl, substituted with the at least one fluoro substituent, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of: -F, -CF3, -CFH2, - CF2H, -CF2CI, -CFCI2, and mixtures thereof, and where -R4is -CF3then -L1- is where the asterisk * indicates the point of connection to -R4, and wherein -R4is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CCI3, -CCI2H, -CBr3, -CBr2H, -Cl3, -CI2H, and mixtures thereof, and -R5- is a covalent bond.

[0128] In some embodiments, -R4is substituted C1-10 alkyl or substituted C2.Cio heteroalkyl, substituted with the at least one fluoro substituent, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of the following : -F, -CF2H, -CF2CI, -CFCI2, and mixtures thereof, wherein -R4is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CC , -CChH, -CBr3, - CBr2H, -C , -CI2H, and mixtures thereof, and -R5- is a covalent bond.

[0129] In some embodiments, -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, substituted with the at least one fluoro substituent, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of the following: -F, - CFH2, -CF2H, -CF2CI, -CFCh, and mixtures thereof, wherein -R4is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CC , -CChH, -CBr3, - CBr2H, -CI3, -CI2H, and mixtures thereof, and -R5- is a covalent bond.

[0130] These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS), but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0131] In some embodiments, -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, wherein -R4comprises a substituted iso-propyl group or a substituted iso-butyl group, and the iso-propyl group or iso-butyl group is substituted with the at least one fluoro substituent, and -R5- is a covalent bond.

[0132] In some embodiments, -R4is substituted C1-10 alkyl or substituted C2 C10 heteroalkyl, wherein -R4comprises a substituted iso-propyl group, and the iso-propyl group is substituted with the at least one fluoro substituent, and -R5- is a covalent bond.

[0133] In preferred embodiments, -R4is selected from one of the following:

[0134]

[0135] In particularly preferred embodiments, -R4is selected from one of the following:

[0136]

[0137] In even more preferred embodiments, -R4is selected from one of the following:

[0138] and where -R4is where the asterisk * indicates the point of connection to -R4.

[0139] 5 In yet even more preferred embodiments, -R4is selected from one of the following: These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS), but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0140] In some embodiments, -R1, -R2and -R3are each independently selected from -H and C1-4 alkyl, preferably -H and methyl, and more preferably -R1is methyl, -R2is -H, and -R3is -H; -L1- is

[0141] , where the asterisk * indicates the point of connection to -R4; R4is substituted Ci- 10 alkyl or substituted C2-C10 heteroalkyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent and is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halos substituents selected from chloro, iodo and bromo.

[0142] In some embodiments, -R1is methyl, -R2is -H, and -R3is -H; -L1- is , where the asterisk * indicates the point of connection to -R4; R4is substituted C1-10 alkyl or substituted C2- C10 heteroalkyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent and is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halos substituents selected from chloro, iodo and bromo.

[0143] In preferred embodiments, -R1is methyl, -R2is -H, and -R3is -H; -L1- is , where the asterisk * indicates the point of connection to -R4; -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl substituted with the at least one fluoro substituent, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R3is selected from one or more of the following: -F, -CF3, -CF2H, -CF2CI, -CFCI2, and mixtures thereof, wherein -R3is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CCI3, -CCI2H, -CBr3, -CBr2H, -Cl3, -CI2H, and mixtures thereof.

[0144] When -R1is methyl, it is thought that the resulting polymer has increased rigidity compared to corresponding acrylates. When R1is methyl, the polymer provides a polymerization rate comparable to other comonomers, despite this increased more rigid polymer product.

[0145] In preferred embodiments, the first polymerizable monomer has the general formula (I):

[0146] 11R1r4R3YJLR2wherein:

[0147] -R1, -R2and -R3are each independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R1is methyl, -R2is -H, and R3is -H;

[0148] -L1- is selected from a covalent bond, where the asterisk * indicates the point of connection to -R4;

[0149] -R4is selected from substituted C6-12 aryl and substituted C1-10 alkyl or substituted C2-C10 heteroalkyl, the aryl group is substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and the alkyl and heteroalkyl groups are substituted with at least one fluoro substituent or at least one group containing a fluoro substituent wherein the at least one fluoro substituent or at least one group containing a fluoro substituent are selected from one or more of the following: -F, -CF3, -CFH2, -CF2H, -CF2CI, -CFCI2, and mixtures thereof, and where -R4is -CF3then -L1- is where the asterisk * indicates the point of connection to -R4, and the aryl, alkyl and heteroalkyl groups are optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo; and where -R4is substituted C6-12 aryl then -R5- is C1-10 alkylene or C2-C10 heteroalkylene, and where -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl then -R5- is a covalent bond.

[0150] These particular fluorinated monomers do not fall under the normal definition of poly and perfluoro alkyl substances (PFAS), but when used in combination with the siloxane containing monomer or prepolymer (second polymerizable component), provide comparable oxygen permeability, wettability, hardness and dimensional stability to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0151] The first polymerizable monomer is preferably selected from pentafluorobenzyl methacrylate (PFBM), pentafluorophenyl methacrylate (PFPM), pentafluorostyrene (PFS), difluoroethyl methacrylate (DFEM), difluorochloroethyl methacrylate, tetrafluoroisopropyl methacrylate, tetrafluorodichloroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, trifluoromethyl methacrylate, trifluoroethyl methacrylate, allylpentafluorobenzene, pentafluorobenzyl acrylate, and mixtures thereof.

[0152] The first polymerizable monomer may be present in the composition in an amount of 5 wt.% or more, such as 10 wt.% or more, 15 wt.% or more, or 20 wt.% or more based on the total weight of the composition.

[0153] The first polymerizable monomer may be present in the composition in an amount of 50 wt.% or less, such as 60 wt.% or less, 65 wt.% or less, 70 wt.% or less, 75 wt.% or less, or 80 wt.% or less based on the total weight of the composition.

[0154] The first polymerizable monomer may be present in the composition in an amount selected from a range with the upper and lower amounts selected from the values given above. For example, the first polymerizable monomer may be present in an amount of from 10 to 75 wt.% based on the total weight of the composition, for example 20 to 70 wt.%.

[0155] The first polymerizable monomer is preferably present in the composition in an amount from 10 to 70 wt.% based on the total weight of the composition, more preferably from 20 to 65 wt.%, and even more preferably from 25 to 60 wt.%.

[0156] The polymerizable composition of the invention comprises a second polymerizable component selected from a polymerizable monomer having an alkenyl group and at least one siloxane group, and a polymerizable pre-polymer having an alkenyl group and at least one siloxane group.

[0157] Generally, the second polymerizable component is a component having an alkenyl group and at least one siloxane group. The second polymerizable component may be divided into monomers and pre-polymers. In this context, a monomer is typically a polymerizable unit which does not include any pre-polymerized repeating units, and a pre-polymer is a polymerizable unit which does include at least one pre-polymerized repeating unit.

[0158] The pre-polymerized repeating unit may be the same or different to the polymerizable part of the pre-polymer. For example, the polymerizble part of the pre-polymer may be an alkenyl group (e.g., a (meth)acrylate group), while the pre-polymerized repeating unit of the pre-polymer may be a polysiloxane group.

[0159] The second polymerizable component may have at least two siloxane groups.

[0160] The second polymerizable component may have at least three siloxane groups.

[0161] In some embodiments, the second polymerizable component further comprises an arylene group.

[0162] In further embodiments, the second polymerizable component further comprises a phenylene group, such as phenyl-1 ,4-ene.

[0163] In some embodiments, the second polymerizable component further comprises an (alkyl)acrylate group comprising the alkenyl group.

[0164] Preferably, the second polymerizable component having an alkenyl group and at least one siloxane group has the general formula (II): wherein:

[0165] -R6, -R7, and -R8are independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R6is methyl, -R7is -H, and -R8is -H; -L2- is selected from a covalent bond, wherein the asterisk * indicates the point of connection to -R9-;

[0166] -R9- is selected from optionally substituted Ce-io arylene, optionally substituted C1-10 alkylene and optionally substituted C2-10 heteroalkylene; where -R9- is optionally substituted Ce-io arylene then -R11- is optionally substituted C1-10 alkylene, optionally substituted C2-10 heteroalkylene, or a covalent bond, and where -R9- is optionally substituted C1-10 alkylene or optionally substituted C2-10 heteroalkylene then -R11- is a covalent bond; and

[0167] -R10is -Si(OSI(R12)3)3, -Si(OSi(R12)3)2R12, -Si(O[Si(R12)2O]rRi2)2R12, or -Si(O[Si(R12)2O]rRi2)3 where each -R12is independently selected from C1-10 alkyl and -OH, and r is 2 to 25.

[0168] Where the second polymerizable component is a second polymerizable monomer, then -R10may be -Si(OSI(R12)3)3, -Si(OSi(R12)3)2R12.

[0169] Where the second polymerizable component is a second polymerizable prepolymer, then -R10may be -Si(O[SI(R12)2O]rRi2)2R12, or -Si(O[SI(R12)2O]rRi2)3. Preferably the siloxane repeating unit is [Si(CH3)2O]r.

[0170] Typically, r is 2 to 25, such as 5 to 20, or 7 to 12.

[0171] The heterolakylene may contain one or more heteroatoms selected from O, N and S.

[0172] The heteroatom(s) of the heteroalkyl and heterolakylene is typically spaced at least one carbon atom away from the alcoholic oxygen atom of -L2- when -L2- is or

[0173] The heteroatom(s) of the heteroalkyl and heterolakylene is not a terminal atom. In other words, the heteroatom(s) are connected to at least two non-hydrogen atoms.

[0174] In some embodiments, -R6, -R7and -R8are all -H. In some embodiments, R6, -R7and -R8are all C1-4 alkyl. In some embodiments, R6, -R7and -R8are all methyl. In some embodiments, -R6is C1-4 alkyl, -R7is -H, and -R8is -H. In some embodiments, -R6is -H, -R7is C1-4 alkyl, and -R8is -H.

[0175] In some embodiments, -R6is methyl, -R7is H and -R8is -H. In some embodiments, -R6is -H, -R7is methyl, and -R8is -H.

[0176] In some embodiments, -L2- is a covalent bond.

[0177] In some embodiments, -L2- is , where the asterisk * indicates the point of connection to -R9-.

[0178] In some embodiments, -L2- is , where the asterisk * indicates the point of connection to -R9-.

[0179] In some embodiments, -L2- , where the asterisk * indicates the point of connection to -R9-.

[0180] In the present invention, -R9- is selected from optionally substituted Ce-io arylene, optionally substituted C1-10 alkylene and optionally substituted C2-10 heteroalkylene.

[0181] -R9- may be optionally substituted with one or more of the following: halo substituents selected from fluoro, chloro, iodo and bromo, groups containing halo substituents selected from fluoro, chloro, iodo and bromo, hydroxyl groups, amino groups, alkyl amino groups, and combinations thereof. In some embodiments, -R9- is optionally substituted Ce-io arylene, and -R11- is optionally substituted C1-10 alkylene, optionally substituted C2-10 heteroalkylene, or a covalent bond. The presence of an arylene group in the second polymerizable component may provide an increase in the oxygen permeability of the resulting polymer and ophthalmic lens.

[0182] -R11- may be optionally substituted with one or more of the following: halo substituents selected from fluoro, chloro, iodo and bromo, groups containing halo substituents selected from fluoro, chloro, iodo and bromo, hydroxyl groups, amino groups, alkyl amino groups, and combinations thereof.

[0183] In some embodiments, -R9- is a phenylene, such as phenyl-1 ,4-ene, and -R11- is optionally substituted C1-10 alkylene, optionally substituted C2-10 heteroalkylene, or a covalent bond.

[0184] In some embodiments, -R9- is phenyl-1 , 4-ene, and -R10- is optionally substituted C1-10 alkylene, optionally substituted C2-10 heteroalkylene, or a covalent bond.

[0185] In some embodiments, -R9- is optionally substituted Ce-io arylene, and -R11- is optionally substituted C1-10 alkylene.

[0186] In some embodiments, -R9- is optionally substituted Ce-io arylene, and -R11- is optionally substituted C1-4 alkylene.

[0187] In some embodiments, -R9- is optionally substituted Ce-io arylene, and -R11- is ethylene.

[0188] In preferred embodiments, -R9- is phenylene, such as phenyl-1 , 4-ene, and -R11- is ethylene.

[0189] In some embodiments, -R9- is optionally substituted arylene, and -R11- is optionally substituted C2-10 heteroalkylene.

[0190] In some embodiments, -R9- is optionally substituted Ce-io arylene, and -R11- is optionally substituted C2-6 heteroalkylene.

[0191] In some embodiments, -R9- is optionally substituted Ce-io arylene, and -R11- is a covalent bond.

[0192] In preferred embodiments, -R9- is phenylene, such as phenyl-1 , 4-ene, and -R11- is a covalent bond. In other embodiments, -R9- is selected from optionally substituted C1-10 alkylene and optionally substituted C2-10 heteroalkylene, and -R11- is a covalent bond.

[0193] In some embodiments, -R9- is optionally substituted C1-10 alkylene, and -R11- is a covalent bond.

[0194] In some embodiments, -R9- is optionally substituted C1-4 alkylene, and -R11- is a covalent bond.

[0195] In some embodiments, -R9- is propylene, and -R11- is a covalent bond.

[0196] In some embodiments, -R9- is optionally substituted C2-10 heteroalkylene, and -R11- is a covalent bond.

[0197] In some embodiments, -R9- is optionally substituted C2-6 heteroalkylene, and -R11- is a covalent bond.

[0198] In the present invention, -R10is -Si(OSi(R12)3)3 or-Si(OSi(R12)3)2Ri2, where each -R12is independently selected from C1-10 alkyl and -OH.

[0199] In some embodiments, -R10is -Si(OSi(R12)3)3, where each -R12is independently selected from C1-10 alkyl and -OH.

[0200] In some embodiments, -R10is -Si(OSi(R12)3)3, where each -R12is C1-10 alkyl.

[0201] In some embodiments, -R10is -Si(OSi(R12)3)3, where each -R12is C1-4 alkyl.

[0202] In preferred embodiments, -R10is -Si(OSi(R12)3)3, where each -R12is methyl.

[0203] In some embodiments, -R10is -Si(OSi(R12)3)3, where each -R12is -OH.

[0204] In some embodiments, -R10is -Si(OSi(R12)3)2Ri2, where each -R12is independently selected from C1-10 alkyl and -OH.

[0205] In some embodiments, -R10is -Si(OSi(R12)3)2Ri2, where each -R12is C1-10 alkyl.

[0206] In some embodiments, -R10is -Si(OSi(R12)3)2Ri2, where each -R12is C1-4 alkyl.

[0207] In preferred embodiments, -R10is -Si(OSi(R12)3)2Ri2, where each -R12is methyl.

[0208] In some embodiments, -R10is -Si(OSi(R12)3)2Ri2, where each -R12is -OH. In the first embodiment, the second polymerizable component is preferably trisiloxane, 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS), 3- [Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS), ), tris(trimethylsilyloxy)-[2-(4- vinylphenyl)ethyl]silane (Styrylethyl TRIS), [2-hydroxy-3-[3-[methyl- bis(trimethylsilyloxy)silyl]propoxy]propyl] prop-2-enoate (SIGMA), methacryloxypropylbis(trimethylsiloxy)silanol, and mixtures thereof.

[0209] In a second embodiment, the second polymerizable component is the polymerizable prepolymer having an alkenyl group and at least one siloxane group.

[0210] In some embodiments, the polymerizable pre-polymer has an alkenyl group and at least one siloxane group, wherein the polymerizable pre-polymer further comprises an (alkyl)acrylate group comprising the alkenyl group.

[0211] In some embodiments, the polymerizable pre-polymer is a polydimethylsiloxane connected to an (alkyl)acrylate group comprising the alkenyl group.

[0212] In some embodiments, the second polymerizable component is preferably a mono(meth)acryalted polydimethylsiloxane pre-polymer. The mono(meth)acryalted polydimethylsiloxane pre-polymer typically includes the (meth)acrylate component at the terminal of the pre-polymer. The pre-polymerized part of the pre-polymer is preferably the siloxane part of the pre-polymer.

[0213] In some embodiments, the second polymerizable component is preferably selected from monomethacrylated polydimethylsiloxane, monomethacryloxypropyl terminated polydimethylsiloxane, methacryloxypropyl T-structure siloxane, and mixtures thereof.

[0214] The pre-polymer may include 2 or more repeating units, preferably 5 or more, more preferably 10 or more, yet more preferably 20 or more repeating units. The pre-polymer may include 55 or less, preferably 50 or less, more preferably 40 or less, yet more preferably 30 or less repeating units.

[0215] The pre-polymer may include a number of repeating units in an amount selected from a range with the upper and lower amounts selected from the values given above. For example, the prepolymer may include 2 to 55 repeating units, preferably 5 to 40 repeating units, more preferably 10 to 30 repeating units. Preferably the pre-polymer includes about 25 repeating units. The number of repeating units described above is typically the number average number of repeating units. The number average repeating units may be measured by any suitable means, such as by dividing the number average molecular weight by the molecular weight of the repeating unit.

[0216] The repeating unit may be a polysiloxane. In such embodiments, then -R10in Formula (II) may be -Si(O[Si(12)2O]ri2)212, or -Si(O[SI(12)2O]ri2)3. Preferably the siloxane repeating unit is [Si(CH3)2O]r. Typically, r is 2 to 25, such as 5 to 20, or 7 to 12.

[0217] The weight average molecular weight (Mw) of the polymerizable pre-polymer may be at least 150, such as at least 500, at least 1000, or at least 2000. The Mwof the vinylic pre-polymer may be at most 5000, at most 4000, or at most 3000.

[0218] The number average molecular weight (Mn) of the polymerizable pre-polymer may be at least 150, such as at least 500, at least 1000, or at least 2000. The Mnof the vinylic pre-polymer may be at most 5000, at most 4000, or at most 3000.

[0219] The Mw and Mnof the polymer may be measured using any suitable method. For example, gel permeation chromatography. The Mwand Mnmay be calculated as described in ISO 16014:2019.

[0220] In the first and second embodiments, the second polymerizable component may be present in the composition in an amount of 5 wt.% or more, such as 10 wt.% or more, 15 wt.% or more, or 20 wt.% or more based on the total weight of the composition.

[0221] The second polymerizable component may be present in the composition in an amount of 55 wt.% or less, such as 65 wt.% or less, 75 wt.% or less, or 85 wt.% or less based on the total weight of the composition.

[0222] The second polymerizable component may be present in the composition in an amount selected from a range with the upper and lower amounts selected from the values given above. For example, the second polymerizable component may be present in an amount from 10 to 75 wt.% based on the total weight of the composition, for example 20 to 70 wt.%.

[0223] In the first embodiment, the second polymerizable component is preferably present in the composition in an amount from 10 to 70 wt.% based on the total weight of the composition, more preferably from 20 to 65 wt.%, and even more preferably from 25 to 60 wt.%. In the second embodiment, the second polymerizable component is preferably present in the composition in an amount from 10 to 70 wt.% based on the total weight of the composition, more preferably from 10 to 65 wt.%, and even more preferably from 10 to 40 wt.%.

[0224] The amount of first polymerizable monomer may be present in the composition in an amount from 10 to 75 wt.% based on the total weight of the composition; and the second polymerizable component in the composition may be present in an amount from 10 to 75 wt.% based on the total weight of the composition.

[0225] The amount of first polymerizable monomer may be present in the composition in an amount from 20 to 65 wt.% based on the total weight of the composition; and the second polymerizable component which is a polymerizable monomer may be present in an amount from 10 to 65 wt.% based on the total weight of the composition, preferably 20 to 65 wt.%.

[0226] The amount of first polymerizable monomer may be present in the composition in an amount from 25 to 60 wt.% based on the total weight of the composition; and the second polymerizable component which is a polymerizable pre-polymer may be present in an amount from 25 to 60 wt.% based on the total weight of the composition, preferably 10 to 40 wt.%.

[0227] The weight ratio between the first polymerizable monomer and the second polymerizable component may be from 3:1 to 1 :3, preferably from 2:1 to 1 :2, more preferably from 1.5:1 to 1 :1.5. Typically, the weight ratio between the first polymerizable monomer and the second polymerizable component is about 1 :1.

[0228] The polymerizable composition may have from 5 to 95 wt.%, such as from 10 to 70 wt.%, by weight of the first polymerizable monomer and from 5 to 95 wt.%, such as from 10 to 70 wt.%, by weight of the second polymerizable component. The remaining portion of the polymerizable composition may comprise other monomer components and / or conventional polymerization agents as described below.

[0229] The polymerizable composition of the invention may further comprise one or more of a third polymerizable monomer, and / or one or more of a fourth polymerizable component, and / or one or more of a fifth monomer, for copolymerization with the first polymerizable monomer and the second polymerizable component. The third polymerizable monomer and / or the fourth polymerizable component and / or fifth polymerizable monomer, may be used to adjust the physical and / or optical properties of the polymer product from the composition, as described below. The third polymerizable monomer may be selected so as to increase the tensile strength of the resulting polymer, for example by resisting deformation under load.

[0230] In some embodiments the polymerizable composition comprises one or more third polymerizable monomers for copolymerization with the first polymerizable monomer and the second polymerizable component, wherein the third monomer has at least one alkenyl group and differs from each of the first polymerizable monomer and second polymerizable component.

[0231] The third polymerizable monomer may be a monomer having an (alkyl)acrylate group, such as methacrylate group, for polymerization with the first polymerizable monomer and second polymerizable component, wherein the (alkyl)acrylate group comprises the alkenyl group.

[0232] The third polymerizable monomer may have an aryl group, such as a phenyl group. Polymers formed from such compositions have improved optical and mechanical properties, such as lack of haze, good in hand foldability and good unfolding time. Examples of such monomers include di(phenylethyl)methyl acrylate, styrene and 2-phenylethyl acrylate.

[0233] In order to maintain a high overall refractive index whilst maintaining polymer flexibility, it is preferable to employ an acrylate monomer possessing an aromatic aryl group, such as di(phenylethyl)methyl acrylate, 2-phenylethyl acrylate, 2-phenylethyl acrylate, 1 ,4- diphenylbutan-2-yl acrylate, 1 ,4-diphenylbutan-2-yl methacrylate, 1 ,5-diphenylpentan-3-yl acrylate and 1 ,5-diphenylpentan-3-yl methacrylate.

[0234] The third polymerizable monomer is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, ethoxyethyl methacrylate, methoxyethyl methacrylate, methacrylic acid, isobornyl methacrylate, isobornyl acrylate, 2-phenylethyl methacrylate, 2-phenylethyl acrylate, 1 ,4-diphenylbutan-2-yl acrylate, 1 ,4-diphenylbutan-2-yl methacrylate, 1 ,5-diphenylpentan-3-yl acrylate, 1 ,5-diphenylpentan-3-yl methacrylate, hydroxyethyl methacrylate, N-vinyl pyrrolidone, neopentyl methacrylate, styrene, and mixtures thereof.

[0235] Particularly preferred examples of third polymerizable monomers include methyl methacrylate, methacrylic acid hydroxyethyl methacrylate, N-vinyl pyrrolidone, neopentyl methacrylate, and styrene. When present, the third polymerizable monomer may be present in the composition in an amount of 5 wt.% or more, such as 10 wt.% or more, 15 wt.% or more, 20 wt.% or more, 25 wt.% or more, or 35 wt.% or more based on the total weight of the composition.

[0236] When present, the third polymerizable monomer may be present in the composition in an amount of 55 wt.% or less, such as 65 wt.% or less, 75 wt.% or less, or 85 wt.% or less based on the total weight of the composition.

[0237] When present, the third polymerizable monomer may be present in the composition in an amount selected from a range with the upper and lower amounts selected from the values given above. For example, the third polymerizable monomer may be present in an amount from 5 to 75 wt.% based on the total weight of the composition, preferably 5 to 50 wt.%, more preferably 1 to 40 wt.%, and yet more preferably 5 to 30 wt.%.

[0238] The third polymerizable monomer may be present in the polymerizable composition at a great or lesser amount than the first polymerizable monomer and / or the second polymerizable component (based on wt.% or mole amount).

[0239] The fourth polymerizable component is a crosslinking component. The crosslinking component is suitable for forming crosslinks with polymerizable monomers and polymerizable components in the polymerizable composition. Typically, the fourth polymerizable component is provided with two or more reactive functional groups, such as olefinic groups, for reaction with suitable functionality on the first polymerizable monomer, and / or the second polymerizable component, and / or the third polymerizable monomer, and / or the fifth polymerizable monomer, where present. The fourth polymerizable component may be provided with functional groups for cross-reactivity between fourth polymerizable molecules.

[0240] Preferably the reactive functional groups of the fourth polymerizable component are unsaturated functional groups such as alkenyl groups. The fourth polymerizable component may be used to generate a three dimensional polymeric network in the polymerized product. The level of crosslinking monomer in the polymerizable composition may be adjusted to alter the material properties of the resulting polymer, most particularly the flexural strength, flexural modulus, and deformation at break parameters.

[0241] In some embodiments, the polymerizable composition further comprises a fourth polymerizable component for forming crosslinks with the polymerizable monomers and the second polymerizable component in the polymerizable composition, wherein the fourth polymerizable monomer is selected from a polymerizable monomer having at least two alkenyl groups, and a polymerizable pre-polymer having at least two alkenyl groups. In some embodiments, the fourth polymerizable component comprises at least one substituted arylene group having at least one fluoro substituent or fluoro-containing substituent group.

[0242] In some embodiments, the fourth polymerizable component comprises an (alkyl)acrylate group comprising one of the alkenyl groups.

[0243] In some embodiments, the fourth polymerizable component comprises at least two (alkyl)acrylate groups each comprising one of the two alkenyl groups, respectively.

[0244] In some embodiments, the fourth polymerizable component is a polymerizable monomer having at least two alkenyl groups.

[0245] The polymerizable monomer having at least two alkenyl groups may comprise at least one substituted arylene group substituted with at least one fluoro substituent or fluoro-containing substituent group.

[0246] The polymerizable monomer having at least two alkenyl groups may comprise at least one substituted phenylene group substituted with least one fluoro substituent or fluoro-containing substituent group.

[0247] The polymerizable monomer having at least two alkenyl groups may preferably comprise at least one 2,3,5,6-tetrafluoro-1 ,4-phenylene group.

[0248] The polymerizable monomer having at least two alkenyl groups may comprise at least one siloxane group.

[0249] The polymerizable monomer having at least two alkenyl groups may comprise at least two (alkyl)acrylate groups each comprising one of the two alkenyl groups, respectively.

[0250] The polymerizable monomer having at least two alkenyl groups may comprise at least one substituted arylene group substituted with at least one fluoro substituent or fluoro-containing substituent group and at least one (alkyl)acrylate group comprising one of the alkenyl groups.

[0251] The polymerizable monomer having at least two alkenyl groups may comprise at least one substituted phenylene group substituted with least one fluoro substituent or fluoro-containing substituent group and at least one (alkyl)acrylate group comprising one of the alkenyl groups. The polymerizable monomer having at least two alkenyl groups may comprise at least one 2,3,5,6-tetrafluoro-1 ,4-phenylene group and at least one (alkyl)acrylate group comprising one of the alkenyl groups.

[0252] The polymerizable monomer having at least two alkenyl groups may preferably comprise at least one 2,3,5,6-tetrafluoro-1 ,4-phenylene group and at least two (alkyl)acrylate group each comprising one of the two alkenyl groups, respectively.

[0253] The polymerizable monomer having at least two alkenyl groups may comprise at least one siloxane group and at least one (alkyl)acrylate group comprising one of the alkenyl groups.

[0254] The polymerizable monomer having at least two alkenyl groups may comprise at least one siloxane group and at least two (alkyl)acrylate groups each comprising one of the two alkenyl groups, respectively.

[0255] In other embodiments, the fourth polymerizable component is a polymerizable pre-polymer having at least two alkenyl groups.

[0256] The polymerizable pre-polymer having at least two alkenyl groups may comprise at least one siloxane group.

[0257] The polymerizable pre-polymer having at least two alkenyl groups may comprise at least one (alkyl)acrylate group comprising one of the alkenyl groups.

[0258] The polymerizable pre-polymer having at least two alkenyl groups may comprise at least two (alkyl)acrylate groups each comprising one of the alkenyl groups, respectively.

[0259] The polymerizable pre-polymer having at least two alkenyl groups may comprise at least one siloxane group and at least one (alkyl)acrylate group comprising one of the alkenyl groups.

[0260] The polymerizable pre-polymer having at least two alkenyl groups may comprise at least one siloxane group and at least two (alkyl)acrylate groups each comprising one of the alkenyl groups, respectively.

[0261] The polymerizable pre-polymer having at least two alkenyl groups may be a polydimethylsiloxane connected to two (alkyl)acrylate groups each comprising one of the alkenyl groups, respectively. A preferred example when the fourth polymerizable component is the polymerizable prepolymer having at least two alkenyl groups, includes, but is not limited to, bis(methacryloxy)butyl polydimethylsiloxane.

[0262] The weight average molecular weight (Mw) of the polymerizable pre-polymer having at least two alkenyl groups may be at least 300, at least 500 or at least 1000. The Mwof the vinylic prepolymer may be at most 5000, at most 3000, or at most 2000. The Mwis measured as described herein, such as using the methods described in ISO 16014:2019.

[0263] The fourth polymerizable component is preferably polyethylene glycol dimethacrylate (PEG chain Mw200-2,000), polyethylene glycol diacrylate (PEG chain Mw200-2,000), polypropylene glycol dimethacrylate (PPG chain Mw250-2,500), polypropylene glycol diacrylate (PPG chain Mw250-2,500), ethylene glycol dimethacrylate, ethyleneglycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl acrylate, allyl methacrylate, 1 ,3-propanediol dimethacrylate, di-allyl maleate, 1 ,4-butanediol dimethacrylate and 1 ,4-butanediol diacrylate, 1 ,3-propanediol diacrylate, 1 ,3-propanediol dimethacrylate, 1 ,4-butanediol dimethacrylate, 1 ,6- hexanediol diacrylate, 1 ,6-hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, butylene glycol dimethacrylate, butylene glycol diacrylate, thio-diethylene glycol diacrylate, thiodiethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and diacrylates and dimethacrylates of bisphenol A, bisphenol A ethoxylate (1- 3EO / phenol), bisphenol A propoxylate (1-3EO / phenol). Other examples of the fourth polymerizable component include, but are not limited to A / ,A / ’-dihydroxyethylene bisacrylamide, diallyl phthalate, triallyl cyanurate, divinylbenzene, ethylene glycol divinyl ether, A / ,A / -methylene- bis-(meth)acrylamide, sulfonated divinylbenzene, divinylsulfone, [2,3,5,6-tetrafluoro-4-(2- methylprop-2-enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate, [2,3,5,6-tetrafluoro-4-(2- methylprop-2-enoyloxy)phenyl] 2-methylprop-2-enoate, [2,3,5,6-tetrafluoro-4-[2,3,5,6-tetrafluoro- 4-(2-methylprop-2-enoyloxy)phenyl]phenyl] 2-methylprop-2-enoate, 1 ,2,4,5-tetrafluoro-3,6- divinyl-benzene, N-vinyl pyrrolidinone, p-vinylbenzyl methacrylate, bis(methacryloxy)butylpolydimethylsiloxane, 1 ,3-Bis(3-(methacryloxy)propyl)-1 ,1 ,3,3- tetrakis(trimethylsiloxy)disiloxane, [difluoro(2-methylprop-2-enoyloxy)methyl] 2-methylprop-2- enoate, [3,3,3-trifluoro-2-(2-methylprop-2-enoyloxy)-1 ,1 ,2-tris(trifluoromethyl)propyl] 2- methylprop-2-enoate, [3,3,3-trifluoro-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate, [2,2,2-trifluoro-1-(trifluoromethyl)-1-[3-[2,2,2-trifluoro-1-(2-methylprop-2-enoyloxy)-1- (trifluoromethyl)ethyl]phenyl]ethyl] 2-methylprop-2-enoate and 1 ,3,5-triallyl-1 ,3,5-triazine- 2, 4, 6(1 / 7,3 / 7,5 / 7)-trione, and mixtures thereof.

[0264] Preferably, the fourth polymerizable component may be selected from one or more of:

[0265]

[0266]

[0267] More preferably, the fourth polymerizable component is selected from one or more of:

[0268] Even more preferably, the fourth polymerizable component is selected from one or more of: In preferable embodiments, the fourth polymerizable component is:

[0269] When the fourth polymerizable component is [2,3,5,6-Tetrafluoro-4-(2-methylprop-2- enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate, this may provide comparable oxygen permeability, to PFAS monomers. Thus, such compounds may provide a suitable alternative to the use of PFAS compounds in preparing ophthalmic lenses.

[0270] This disclosure also provides a compound having the following structure:

[0271] In some embodiments, the compound having the following structure: is for use in an ophthalmic lens comprising a polymer obtained from curing a polymerizable composition.

[0272] The compound may also be known as [2,3,5,6-Tetrafluoro-4-(2-methylprop-2- enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate.

[0273] In some embodiments, the compound, [2,3,5,6-Tetrafluoro-4-(2-methylprop-2- enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate, is for use in an ophthalmic lens comprising a polymer obtained from curing a polymerizable composition.

[0274] In some embodiments, the compound is used as a crosslinker. A crosslinker is suitable for forming crosslinks with polymerizable monomers and / or polymerizable components in a polymerizable composition. Typically, crosslinkers are provided with two or more reactive functional groups, such as olefinic groups, for reaction with suitable functionality on polymerizable monomers and / or polymerizable components in a polymerizable composition. When present, the fourth polymerizable component may be present in the composition in an amount of 0.1 wt.% or more, such as 0.2 wt.% or more, 2 wt.% or more, 5 wt.% or more, or 15 wt.% or more based on the total weight of the composition.

[0275] When present, the fourth polymerizable component may be present in the composition in an amount of 50 wt.% or less, such as 25 wt.% or less, 20 wt.% or less, or 15 wt.% or less based on the total weight of the composition.

[0276] When present, the fourth polymerizable component may be present in the composition in an amount selected from a range with the upper and lower amounts selected from the values given above. For example, the fourth polymerizable component may be present in an amount from 0.1 to 50 wt.% of the total weight of the composition, preferably 0.1 to 25 wt.%, more preferably 0.1 to 20 wt.%, and yet more preferably 5 to 15 wt.%.

[0277] A fifth polymerizable monomer may be present in the polymerizable composition. The fifth polymerizable monomer is a hydrophilic monomer. The fifth polymerizable monomer is suitable for polymerization with the first polymerizable monomers, and / or the second polymerizable component and additional polymerizable monomers and components incorporated into the formulation.

[0278] The fifth polymerizable monomer may have a hydroxy group, such as hydroxyalkyl group, an amino group, including a carboxamide, or an alkoxy group, such as a poly(oxyalklene) group.

[0279] The fifth polymerizable monomer may have an (alkyl)acrylate group for polymerization with the first polymerizable monomer and second polymerizable component, and other polymerizable monomers and polymerizable components, where present. The fifth polymerizable monomer may have a (meth)acrylate group, for example a methacrylate or an acrylate groups.

[0280] The fifth polymerizable monomer is preferably 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, A / -vinyl pyrrolidin-2-one, methacrylic acid, acrylic acid, acrylamide, methacrylamide, A / , A / - dimethyl acrylamide, A / -methyl-A / -vinylacetamide, 2-hydroxy-3-phenoxypropyl acrylate, glycerol monomethacrylate, polyethylene glycol monomethacrylate (PEG chain Mw= 200-2,000), polyethylene glycol methyl ether methacrylate (PEG chain Mw= 200-2,000), polyethylene glycol monoacrylate (PEG chain Mw= 200-2,000), polyethylene glycol methyl ether acrylate (PEG chain Mw= 200-2,000) and A / -(2-hydroxypropyl) methacrylamide and mixtures thereof. It is noted that the third polymerizable monomer and fourth polymerizable component may also be hydrophilic or may include hydrophilic functionality. Such monomers and components may also modulate the refractive index and the hydrophilicity of the polymer product, as described above for the fifth polymerizable monomer.

[0281] When present, the fifth polymerizable monomer may be present in the composition in an amount of 0.1 wt.% or more, such as 0.2 wt.% or more, 0.5 wt.% or more, 1 wt.% or more, 2 wt.% or more, 5 wt.% or more, or 10 wt.% or more based on the total weight of the composition.

[0282] When present, the fifth polymerizable monomer may be present in the composition in an amount of 50 wt.% or less, such as 40 wt.% or less, 25 wt.% or less, or 15 wt.% or less based on the total weight of the composition.

[0283] When present, the fifth polymerizable monomer may be present in the composition in an amount selected from a range with the upper and lower amounts selected from the values given above. For example, the fifth polymerizable monomer may be present in an amount from 0.1 to 50 wt.%, preferably 0.1 to 15 wt.%.

[0284] The polymerizable composition may further comprise conventional compounds for use on polymerization including, but not limited to, a thermally- or light-activated polymerization initiator (preferably in an amount of 5 wt.% or less based on the total weight of the composition), a “fixable”, for example by free-radical vinyl-polymerization, UV-light absorber (also known as UV blockers, and are present preferably in an amount of 5 wt.% or less based on the total weight of the composition), a “fixable” blue-light absorber (preferably in an amount of 0.5 wt.% or less of the total weight of the composition), a strengthening agent, or a combination thereof. In one embodiment, the conventional compound comprises a functional group that is suitable for polymerization with the first polymerizable monomer and the second polymerizable component, and / or the third polymerizable monomer, fourth polymerizable component and fifth polymerizable monomer, where present.

[0285] As used herein, the term “fixable” is used in relation to a compound that may be incorporated into the polymer upon polymerization of the polymerizable composition. Thus, a fixable compound is suitable for reaction with one or more of the first, third and fifth polymerizable monomers, and second and fourth polymerizable components, where present. Exemplary fixable monomers include those having vinyl functionalities (such as alkenyl groups) for participation in, for instance, free-radical polymerization with other vinyl-containing monomers, such as the first polymerizable monomer described herein. Suitable UV-light absorbers are preferably benzoylphen-2-ol or 2-(2 / 7-benzo[d][1 ,2,3]triazol-2- yl)phenol chromophore, such as 2-[3’-(2’ / 7-benzotriazol-2’-yl)-4’-hydroxyphenyl]- ethylmethacrylate, 2-(4’-benzoyl-3’-hydroxyphenoxy)ethyl acrylate , 2-hydroxy-4- allyloxybenzophenone, 2-(2’-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, p-(4- benzotriazoyl-3-hydroxyphenoxy)ethylacrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloyloxy-2-hydroxybenzophenone, 2-(2’-methacryloyloxy-5’- methylphenyl)benzotriazole, 2-(2’-hydroxy-5’-methacryloxyethylphenyl)-2H-benzotriazole, 2-[3’- tert-butyl-2’-hydroxy-5’-(3”-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 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, 2-[3’-tert-butyl-2’-hydroxy-5’-(3”- methacyloyloxypropoxy)phenyl]-5-chlorobenzotriazole, 2-(2’-hydroxy-5'- methacryloyloxyethylphenyl)-2 / 7-benzotriazole and 2-(2'-hydroxy-3'-methallyl-5'- methylphenyl)benzotriazole. A preferred monomer as a UV-light absorber is 2-(4’-benzoyl-3’- hydroxyphenoxy)ethyl acrylate . Suitable dyes are preferably 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3).

[0286] The polymerizable composition may comprise a thermally- or photo-activated polymerization initiator. Preferably, the initiator is a free-radical polymerization initiator.

[0287] When present, the polymerization initiator may be present in the composition in an amount of 2.0 wt.% or less, such as 1 .0 wt.% or less, or 0.5 wt.% or less based on the total weight of the composition.

[0288] When present, the polymerization initiator may be present in the composition in an amount from 0.1 to 2.0 wt.%, preferably 0.1 to 1 .0 wt.%, more preferably 0.1 to 0.50 wt.%, and yet more preferably 0.05 to 0.30 wt.% based on the total weight of the composition.

[0289] Free-radical polymerization of the polymerizable composition may be initiated thermally using a thermal free radical initiator such as peroxide, peroxidedicarbonate or azo-based initiators. Examples of peroxide or peroxidedicarbonate based initiators include, but are not limited to, dilauroyl peroxide, didecanoyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxybenzoate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate. Examples of azo-based initiators include, but are not limited to, 1 ,1'-azobiscyanocyclohexane, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2’-azobisisobutyronitrile and 2,2'-azobis(2-methylbutyronitrile).

[0290] Preferably, the thermal free radical initiator is selected from tert-butyl peroxybenzoate, 2,2’-azobisisobutyronitrile (AIBN), and combinations thereof. Photoactivated free-radical polymerization of the polymerizable composition may be initiated by a photoinitiator, such as CIBA’s Irgacure® 1800 [comprising 25% bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethyl-pentylphosphine oxide and 75% 1-hydroxy-cyclohexyl-phenyl ketone], Irgacure® 184 [comprising 100% 1-hydroxy-cyclohexyl-phenyl ketone], Irgacure® 819 [comprising 100% bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide], Irgacure® 2959 [comprising 100% 1-[4-(2- hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one], Darocur® MBF [comprising 100% phenyl glyoxylic acid methyl ester], Darocur® TPO [comprising 100% 2,4,6-trimethylbenzoyl- diphenylphosphine oxide] and Darocur® 1173 [comprising 100% 2-hydroxy-2-methyl-1-phenyl- propan-1-one].

[0291] In embodiments where thermal polymerization is employed in the polymerization process, the preferred free-radical initiator is 2,2’-azobisisobutyronitrile (AIBN). Where photo-initiated free- radical polymerization is employed to fabricate the hydrophobic-acrylic polymer composition, the preferred initiator bis(2, 4, 6-trimethylbenzoyl)-phenyl-phosphineoxide (for example, Irgacure 819).

[0292] The polymerizable composition may further comprise a diluent. The diluent may aid the processing of the polymer after polymerization, particularly during the expulsion of extractable contaminants, such as residual monomers, by treatment with an appropriate solvent.

[0293] It will be appreciated that the total amount of first polymerizable monomer, second polymerizable component, third polymerizable monomer, fourth polymerizable component and fifth polymerizable monomer, where present, additional compounds where present, and diluent, where present, does not exceed 100 wt. %.

[0294] Polymers

[0295] The invention provides a polymer obtainable or obtained from the polymerizable composition of the second aspect of the invention. The resin may be a moulded product. The terms ‘resin’ and ‘polymer’ are interchangeable as used herein.

[0296] The polymers are suitable for use in optical materials, such as ophthalmic lenses (e.g. contact lenses or lOLs).

[0297] The polymer of the invention is a polymer obtained or obtainable by polymerization of a polymerizable composition of the invention. The polymerizable composition is as described in the second aspect of the invention. In one embodiment, the polymer is obtained or obtainable by free radical polymerization of a polymerizable composition of the invention. In one embodiment, the polymer is obtained or obtainable by photo-initiated polymerization. The polymer is typically a copolymer comprising repeating units formed from the first polymerizable monomer and the second polymerizable component. The polymer may be a block co-polymer, a statistical (or random) copolymer, or an alternating copolymer. Preferably, the polymer is a random copolymer.

[0298] The polymer may be a linear or branched polymer, and is preferably a linear polymer.

[0299] In some embodiments, the polymer may be a polymer comprising repeating units formed from the first polymerizable monomer and comprises cross-links formed from the second polymerizable component. In alternative embodiments, the polymer may be a polymer comprising repeating units formed from the second polymerizable monomer and comprises cross-links formed from the first polymerizable component.

[0300] The polymer may also include repeating units formed from the third, fourth and / or fifth polymerizable components described above. In addition, or alternatively, the polymer may include cross-links formed from the third, fourth and / or fifth polymerizable components described above.

[0301] In some embodiments, the number of repeating units formed from the first polymerizable monomer present in the polymer as a mole fraction of all the units present is 0.05 or more, such as 0.10 or more, 0.15 or more, or 0.20 or more.

[0302] In some embodiments, the amount of repeating units formed from the first polymerizable monomer present in the polymer as a mole fraction of all the units present is 0.50 or less, such as 0.60 or less, 0.65 or less, 0.70 or less, 0.75 or less, or 0.80 or less.

[0303] The mole fraction for the first polymerizable monomer may a range with the upper and lower amounts selected from the values given above. For example, the mole fraction for the first polymerizable monomer may be from 0.1 to 0.75, preferably 0.2 to 0.6, more preferably 0.3 to 0.5.

[0304] In some embodiments, the amount of repeating units formed from the second polymerizable monomer present in the polymer as a mole fraction of all the units present is 0.05 or more, such as 0.10 or more, 0.15 or more, or 0.20 or more.

[0305] In some embodiments, the amount of repeating units formed from the second polymerizable monomer present in the polymer as a mole fraction of all the units present is 0.50 or less, such as 0.60 or less, 0.65 or less, 0.70 or less, 0.75 or less, or 0.80 or less. The mole fraction for the second polymerizable monomer may a range with the upper and lower amounts selected from the values given above. For example, the mole fraction for the second polymerizable monomer may be from 0.1 to 0.75, preferably 0.2 to 0.6, more preferably 0.3 to 0.5.

[0306] In some embodiments, the polymers of the invention comprise a unit of formula (la): where -R1, -R2, -R3, -R4, and -L1-, are as defined for the first polymerizable monomers of formula

[0307] (I)-

[0308] In one embodiment, the polymer contains ‘n’ units of formula (la). The n units of formula (la) may be sequential or separated by other formula units (e.g., units of formula (Ila)). n may be 50 or more, preferably 100 or more, more preferably 500 or more, yet more preferably 1000 or more, n may be 10,000 or less, preferably 5000 or less, more preferably 1 ,000 or less, yet more preferably 500 or less. n may be selected from a range with the upper and lower amounts selected from the values given above. For example, n may be 50 to 10,000, preferably 500 to 5,000, more preferably 1 ,000 to 3,000.

[0309] In one embodiment, the amount of unit (la) present in the polymer as a mole fraction of all the units present is 0.05 or more, such as 0.10 or more, 0.15 or more, or 0.20 or more. The amount of unit (la) present in the polymer as a mole fraction may be 0.50 or less, such as 0.60 or less, 0.65 or less, 0.70 or less, 0.75 or less, or 0.80 or less.

[0310] The final mole fraction of (la) in the polymer may be altered by, for example, increasing or decreasing the amount of monomer of formula (I) in the polymerizable composition.

[0311] In some embodiments, the polymers of the invention comprise a unit of formula (Ila): where -R5, -R6, -R7, -R8, -R9and -L2- are as defined for the second polymerizable components of formula (Ila).

[0312] In one embodiment, the polymer contains ‘m’ units of formula (Ila). The m units of formula (Ila) may be sequential or separated by other formula units (e.g., units of formula (la)). m may be 50 or more, preferably 100 or more, more preferably 500 or more, yet more preferably 1000 or more, m may be 10,000 or less, preferably 5000 or less, more preferably 1 ,000 or less, yet more preferably 500 or less. m may be selected from a range with the upper and lower amounts selected from the values given above. For example, m may be 50 to 10,000, preferably 500 to 5,000, more preferably 1 ,000 to 3,000.

[0313] In one embodiment, the polymer contains one or more units of formula (Ila).

[0314] In one embodiment, the amount of unit (Ila) present in the polymer as a mole fraction of all the units present is 0.05 or more, such as 0.10 or more, 0.15 or more, or 0.20 or more. The amount of unit (Ila) present in the polymer as a mole fraction may be 0.50 or less, such as 0.60 or less, 0.65 or less, 0.70 or less, 0.75 or less, or 0.80 or less.

[0315] The final mole fraction of (Ila) in the polymer may be altered by, for example, increasing or decreasing the amount of monomer of formula (Ila) in the polymerizable composition.

[0316] The mole fraction may be determined from, for example,1H and / or13C NMR measurements of the polymer product. Additionally or alternatively, the mole fraction may be surmised from the amount of first polymerizable monomer in the polymerizable composition as a fraction of all the polymerizable monomers and polymerizable components present.

[0317] In one embodiment, the weight average molecular weight (Mw) of a linear polymer-chain is at least 25,000 Da, or is at least 125,000 Da, or is least 250,000 Da, or is at least 1 ,250,000 Da. The chain length refers to the backbone length and does not refer to sections of polymer passing through branch points. The Mwof a linear polymer-chain may be measured using standard techniques, for example from Tg measurements of the polymer, such as described by Thermal Analysis Consulting.

[0318] In some embodiments, the polymer has an oxygen permeability (Dk) of 30 Barrers or more, such as 50 Barrers or more, 60 Barrers or more, 70 Barrers or more, or 80 Barrers or more. Preferably, the polymer has an oxygen permeability (Dk) of 100 Barrers or more, such as 120 Barrers or more, or 140 Barrers or more.Oxygen permeability (Dk) may be measured using ISO 18369-4:2017, as described in the example section.

[0319] Refractive Index of the polymer may be about 1 .40 to 1 .50. Preferably, the refractive index is 1.41 to 1.45, more preferably 1.42 to 1.44.

[0320] The refractive index may be measured with an ABBE refractometer using ISO 18369-4, as described in the examples section.

[0321] Initial Sessile Contact angle may be 110° or less, preferably 105° or less, more preferably 100° orless.

[0322] Sessile Contact angle after 1 week may be 100° or less, preferably 95° or less, more preferably 90° or less.

[0323] Sessile Contact angle is measured as described in the examples section.

[0324] Impact hardness of the polymer may be 70 or more, preferably 75 or more, more preferably 80 or more.

[0325] Rest hardness of the polymer may be 70 or more, preferably 75 or more, more preferably 80 or more.

[0326] Flexural Modulus may be 900 MPa or more, preferably 1000 MPa or more, more preferably 1100 MPa or more.

[0327] The mechanical properties (hardness and flexural modulus) were obtained using ANSI Z80.20, as described in the examples section.

[0328] Method of Preparing a Polymer

[0329] Generally, the invention is a method of polymerizing the polymerizable composition as described herein. The method typically comprises curing the polymerizable composition. In some embodiments, the method is a method of forming an optical material, comprising curing a polymerizable composition to form an optical material. In preferred embodiments, the optical material is an ophthalmic lens.

[0330] The polymer may be formed in a mould to provide a polymer product having a desired shape. For example, the polymer may be polymerized in a lens-shaped mould to yield a lens.

[0331] Alternatively, the polymer may be polymerized in a button or rod-shaped mould to yield a polymer button or rod. The button or rod may be subsequently machined to form a lens. Such methods are described in further detail below.

[0332] In a fourth aspect of the invention there is provided a method of forming an ophthalmic lens, wherein the method comprises the steps of: i) curing the polymerizable composition of the second aspect in a mould to form a molded product; ii) optionally annealing the moulded product; and iii) working the molded product to form an ophthalmic lens.

[0333] In some embodiments, the molded product is a polymer rod. In some embodiments, the working step comprises lathing the polymer rod. Preferably, the polymer rod is lathed to form polymer buttons. The polymer buttons may then be further shaped (e.g., machined, polished) to forma a ophthalmic lens.

[0334] In such embodiments, the method may comprise the steps of:

[0335] I) curing the polymerizable composition of the second aspect in a substantially rod-shaped mould to form a polymer rod; ii) optionally annealing the polymer rod; and iii) working the polymer rod to form an ophthalmic lens.

[0336] In some embodiments, the molded product is a lens blank. In some embodiments, the working step comprises machining the lens blank.

[0337] In such embodiments, the method may comprise the steps of: i) curing the polymerizable composition of the second aspect in a button-shaped mould to form a lens blank; ii) optionally annealing the lens blank; and iii) working the lens blank to form an ophthalmic lens. In some embodiments, the molded product is a ophthalmic lens. In some embodiments, the working step comprises finishing the ophthalmic lens (e.g., machining or polishing the ophthalmic lens).

[0338] In such embodiments, the method may comprise the steps of: i) curing the polymerizable composition of the second aspect in lens shaped mould to form a ophthalmic lens; ii) optionally annealing the ophthalmic lens; and iii) optionally working the ophthalmic lens.

[0339] In some embodiments the method of preparing the polymer of the third aspect of the invention comprise the steps of:

[0340] (i) combining the polymerizable components to form a polymerizable composition, and

[0341] (ii) curing the polymerizable composition to form a cured polymer; and

[0342] (iii) annealing the cured polymer.

[0343] The step of combining the polymerizable components to form a polymerizable composition may be known as the combining step. The combining step typically includes admixing the first polymerizable monomer and the second polymerizable component.

[0344] In a preferred embodiment, the combining step includes combining: a first polymerizable monomer preferably in an amount from 10 to 70 wt.%, more preferably 20 to 65 wt.%, and yet more preferably 25 to 60 wt.% based on the total weight of the composition; and a second polymerizable component of the first embodiment, preferably in an amount from 10 to 70 wt.%, more preferably 20 to 65 wt.%, and yet more preferably 25 to 60 wt.% based on the total weight of the composition; and optionally one or more of the following reagents: a third polymerizable monomer preferably in an amount from 5 to 50 wt.%, more preferably 1 to 40 wt.%, and most preferably 5 to 30 wt.% based on the total weight of the composition; and / or a fourth polymerizable component preferably in an amount in the range in an amount in the range 0.1 to 25 wt.%, more preferably 0.1 to 20 wt.%, and yet more preferably 5 to 15 wt.% based on the total weight of the composition; and / or polymerization initiator preferably in an amount in the range 0.1 to 1.0 wt.%, more preferably 0.1 to 0.50 wt.%, and yet more preferably 0.05 to 0.30 wt.% based on the total weight of the composition; and / or non-participating solvent.

[0345] In a preferred embodiment, the combining step includes combining: a first polymerizable monomer preferably in an amount from 10 to 70 wt.%, more preferably 20 to 65 wt.%, and yet more preferably 25 to 60 wt.% based on the total weight of the composition; and a second polymerizable component of the second embodiment, preferably in an amount from 10 to 70 wt.%, more preferably 10 to 65 wt.%, and yet more preferably 10 to 40 wt.% based on the total weight of the composition; and optionally one or more of the following reagents: a third polymerizable monomer preferably in an amount from 5 to 50 wt.%, more preferably 1 to 40 wt.%, and most preferably 5 to 30 wt.% based on the total weight of the composition; and / or a fourth polymerizable component preferably in an amount in the range in an amount in the range 0.1 to 25 wt.%, more preferably 0.1 to 20 wt.%, and yet more preferably 5 to 15 wt.% based on the total weight of the composition; and / or polymerization initiator preferably in an amount in the range 0.1 to 1.0 wt.%, more preferably 0.1 to 0.50 wt.%, and yet more preferably 0.05 to 0.30 wt.% based on the total weight of the composition; and / or non-participating solvent.

[0346] The step of curing the polymerizable composition may be known as the “curing step”. This step is also described in the Ophthalmic Lens section below.

[0347] The curing step typically includes heating the polymerizable composition. The polymerizable composition may be heated to from 30 to 90°C, such as 35 to 80°C, preferably 40 to 70°C.

[0348] The curing step typically heats the polymerizable composition for a period of time, such as 24 to 96 hours, such as 48 to 72 hours.

[0349] The step of annealing the cured polymer may be known as the “annealing step”. This step is also described in the Ophthalmic Lens section below.

[0350] The annealing step typically includes heating the cured polymer. The annealing step may be done under a vacuum. The annealing step may heat the polymer from room temperature (i.e. , after the cured polymer has cooled from the curing step). The annealing step may heat the polymer to a temperature greater than that of the curing step. The annealing step may heat the polymer to a temperature of 40 to 130°C, such as 50 to 120°C, preferably 60 to 110°C. The annealing step typically heats the polymer for a period of time under a vacuum, such as 24 to 96 hours, such as 48 to 72 hours. Ophthalmic Lens and Methods for Manufacture

[0351] The first aspect of the present invention provides an ophthalmic lens comprising a polymer obtained from a polymerizable composition as defined in the second aspect of the invention.

[0352] The ophthalmic lens of the invention is preferably a contact lens. Such lenses are placed in intimate contact with the users eye. Some ophthalmic lenses, such as contact lens, reside in intimate contact with a tear film or other liquid film that usually resides between the contact lens and a user’s eye. Examples of ophthalmic lenses include, but are not limited to, contact lenses in all their variants, therapeutic lenses, orthokeratology lenses, scleral lenses, protective lenses, cosmetic lenses, drug delivery devices, and smart lenses.

[0353] In some embodiments, the ophthalmic lens is a contact lens.

[0354] In some embodiments, the ophthalmic lens is an intraocular lens.

[0355] Further aspects of the present invention provide a blank for an ophthalmic lens formed from the polymerizable composition of the second aspect of the invention and preparing an ophthalmic lens of the first aspect of the invention.

[0356] The blank may be formed as a substantially cylindrical polymer product, with the cylinder typically having a circular diameter exceeding that of the altitude of the cylinder. The substantially cylindrical product may be formed from a cast moulding process using a suitable depression mould. The cylindrical polymer product may be worked, for example machined using milling and / or lathe cutting processes familiar to those skilled in the art, until a finished ophthalmic lens is obtained. The working process may also be referred to as machining of a shaped polymer product.

[0357] In some embodiments, the blank for an ophthalmic lens is prepared form a polymerizable composition that is substantially free of non-participating solvent.

[0358] In some embodiments, the blank for an ophthalmic lens is prepared from a polymerizable composition that comprises a predetermined amount of non-participating solvent.

[0359] Alternatively, a mould may be used to fabricate a completely or substantially finished ophthalmic lens directly. Additional machining, typically involving the polishing of the optic portions of the lens, is usually required for a substantially finished ophthalmic lens to produce a useable lens. The present invention also encompasses methods for fabricating a blank for an ophthalmic lens, and methods for fabricating an ophthalmic lens from a lens blank or from a polymer of a previous aspect of the invention.

[0360] A general method for fabricating an ophthalmic lens of the present invention comprises the steps of:

[0361] (a) providing a blank according to the present invention; and

[0362] (b) working the blank so as to form an ophthalmic lens.

[0363] Lens blanks according to the present invention may be manufactured according to any one of the methods described below. Reference to the shape or design of a mould as used herein refers to the shape or design of the part of the mould where the actual polymerization of the polymer takes place.

[0364] A first method of forming a blank for an ophthalmic lens comprises the steps of:

[0365] (a) polymerization of a composition of the present invention in a substantially rod-shaped mould thereby to form a polymer rod; and

[0366] (b) working the polymer rod into a plurality of cylindrical blanks.

[0367] A polymerization reaction on a polymerizable composition of the present invention may be performed in the mould to form the polymer. Alternatively a preformed linear polymer may be placed in the mould and then cured to obtain the desired polymer product. An example of polymerization in the mould is described below in the button moulding method.

[0368] A substantially rod-shaped ( / .e. cylindrical) mould is typically constructed from polypolypropylene, polyethylene, PTFE or glass. The shape and size of the mould determines the diameter of the polymer rod. The diameter for the polymer rod is chosen for the design of the resulting ophthalmic lens to be formed; a larger diameter rod is required for a single piece ophthalmic lens and a smaller diameter rod is sufficient for a two or three-piece design ophthalmic lens. Typically, the polymer rod formed is worked into a series of homogeneous discs as described above. Generally the discs have parallel faces. Alternatively, the polymer rod may be worked into a series of discs wherein one face is concave.

[0369] A method for forming the ophthalmic lens of the first aspect of the invention, may comprise the steps of:

[0370] I) curing the polymerizable composition of the second aspect in a substantially rod-shaped mould thereby to form a polymer rod;

[0371] II) annealing the resulting polymer rod; and ill) lathing the polymer rod into buttons. In an alternative method, a blank for an ophthalmic lens may be formed in a method comprising the step of polymerization of a polymerizable composition according to the invention in a button mould thereby forming a lens blank. A polymerization reaction on the polymerizable composition of the present invention may be performed in the button mould to form the polymer. An uncured polymer may be placed in the mould and cured, as an alternative to this method.

[0372] A method for forming the ophthalmic lens of the first aspect of the invention, may comprise the steps of: i) curing the polymerizable composition of the second aspect of the invention in a button mould thereby forming a lens blank; ii) optionally annealing the resulting polymer; and iii) lathe machining the ophthalmic lens from the lens blank.

[0373] Typically, button moulds consist of an array of button impressions on a pre-formed polypropylene, polyethylene or PTFE sheet. The dimensions of the individual button moulds are determined by the resulting design of the final lens. Button moulds with a larger diameter button are required for a scleral ophthalmic lens, and a smaller diameter button mould is sufficient for a corneal ophthalmic lens.

[0374] The mould-sheet is covered with film, typically comprising polyethylene or polypropylene. The filmcovered mould-sheet is filled with the polymer composition of the present invention and the mould is sealed, for example using a heat-sealing bar apparatus. A monomer formulation may be polymerized in the mould using an oven or, more preferentially, in a water bath thermally equilibrated to the required polymerization temperature.

[0375] Once the polymerization step has been completed, the water bath is allowed to cool and the mould-sheet is removed, cleaned and dried. The film can then be peeled from the mould and the polymerized discs extruded.

[0376] A lens blank obtained using the above moulding methods may be ground and polished such that the dimensions of the disc or blank lies within a stringent tolerance window with respect to the accuracy of both the diameter of the disc and the altitude between the opposing circular faces and their degree of parallelism.

[0377] The present invention also provides a method for preparing an ophthalmic lens, wherein a lens blank is lathe cut and optionally machine milled into a required lens shape. The step of machining a blank or polymer disc to form an ophthalmic lens comprises the following steps:

[0378] (a) lathe machining a first surface of an ophthalmic lens from a lens blank,

[0379] (b) lathe machining a second surface of an ophthalmic lens from the lens blank. In some circumstances it may be preferable to first machine the posterior surface of the contact lens followed by the anterior surface. Alternatively, the anterior surface may be machined first.

[0380] The invention also provides a method of preparing an ophthalmic lens of the invention, such as a contact lens, by direct formation of a partial or complete lens using a mould designed specifically for that purpose. The method may comprise the step of polymerizing a polymerizable composition of the present invention in a mould in order to form an ophthalmic lens, wherein the mould is shaped so as to provide an ophthalmic lens having anterior and / or posterior portions consistent with conferring the desired optical performance (for example, focussing power) onto the polymer article.

[0381] A method for forming the ophthalmic lens may comprise the steps of: i) curing the polymerizable composition; and ii) optionally annealing the resulting polymer.

[0382] As before, the polymerizable composition of the present invention may be polymerized in the mould to form the polymer. As before, an uncured polymer may be placed in the mould and cured, as an alternative method.

[0383] The mould design may encompass the anterior and / or posterior portion of the lens, or the complete lens. If only one lens surface is directly moulded, then the optics of the complementary surface may be subsequently formed by lathing and machine milling, either at room temperature or at a reduced temperature, as described above.

[0384] In another aspect of the inventions there is provided a method of forming a polymeric article by curing a linear polymer prepared from the polymerizable composition of the invention. The linear polymer is thus composed of polymeric units derived from the first monomer of the invention and optionally one or more polymeric units derived from the second, third and fourth monomers for use in the invention. The curing process may also be referred to as a crosslinking procedure.

[0385] In one embodiment, a polymer may be physically “cured” by the formation of an interpenetrating polymer network (IPN). Here the polymer is solubilised with a polymerizable monomer(s) which is / are polymerized to form a second polymer that is co-contingent with the first thereby to provide an interweaving polymer network which is essentially non-divisible (“intermingled”) due to chain entanglement. The polymers within the IPN formulation may optionally each incorporate cross-linking components so as to allow for the introduction of chemical cross-links.

[0386] In a further embodiment, a linear polymer may be formed comprising polymeric units derived from the first monomer of the invention. The linear polymer further comprises functionality that can be interlinked (“cured”) in a subsequent step. The functionality may be present in the polymeric units derived from the first monomer of the invention, and / or it may be present in one or more of the polymeric units derived from the second, third or fourth monomers, where present.

[0387] One example of a reactive monomer suitable for incorporation into a polymer that is to be cured is glycidyl methacrylate. When contained within a polymer, the epoxide functionality of this monomer is capable of forming interlinks with adjacent polymer chains by reaction with a suitable dinucleophile. Examples include, but are not limited to, an alkyldialkoxide, an alkyldimercaptan, an alkyldiamine, an alkyldicarboxylic acid, and an alkyldicarboxylate salt.

[0388] An alternative approach is to incorporate into a linear polymer functionality that is capable of photo-crosslinking. One example of a photoreactive monomer suitable for incorporation into a polymer that is to be cured is 9-anthracene methyl methacrylate. When contained within a polymer, the photoreactive moiety undergoes light-induced 4n + 4n cycloadditon with an adjacent anthracene ring to form a dianthracene linkage.

[0389] Definitions

[0390] Substituents are defined and exemplified below.

[0391] The phrase “optionally substituted” as used herein, pertains to a parent group which may be unsubstituted or which may be substituted.

[0392] Unless otherwise specified, the term “substituted” as used herein, pertains to a parent group which bears one or more substituents. The term “substituent” is used herein in the conventional sense and refers to a chemical moiety which is covalently attached to, or if appropriate, fused to, a parent group. A wide variety of substituents are well known, and methods for their formation and introduction into a variety of parent groups are also well known. The substituents may be selected from the groups listed below.

[0393] Alkyl: The term “alkyl” as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of a saturated hydrocarbon compound, which may be aliphatic or alicyclic (cycloalkyl). The alkyl group may be a C1-20, C1-12, C1-6, C3-6, C1-20, C3-12, C3-5, C3-5, Ci-4 or C1-2 alkyl group. A preferred aliphatic alkyl group is C1-6 alkyl, most preferably C1-4 alkyl. A preferred cycloalkyl group is C3-6 cycloalkyl, most preferably C5-6 cycloalkyl.

[0394] An aliphatic alkyl group may be linear or branched.

[0395] Examples of alkyl groups include, but are not limited to, methyl (Ci), ethyl (C2), propyl (C3), butyl (C4), pentyl (C5), hexyl (C6).

[0396] An example of a substituted alkyl group includes, but is not limited to, perfluorooctyl (CeF ). Such a group may be referred to as a haloalkyl group, such as described herein.

[0397] Examples of linear alkyl groups include, but are not limited to, methyl (Ci), ethyl (C2), n-propyl (C3), n-butyl (C4), n-pentyl (amyl) (C5), n-hexyl (Ce).

[0398] Examples of branched alkyl groups include iso-propyl (C3), iso-butyl (C4), sec-butyl (C4), tert-butyl (C4), iso-pentyl (C5), and neo-pentyl (C5).

[0399] Examples of cycloalkyl groups include, but are not limited to, those derived from: saturated monocyclic hydrocarbon compounds: cyclopropane (C3), cyclobutane (C4), cyclopentane (C5), cyclohexane (Ce), methylcyclopropane (C4), dimethylcyclopropane (C5), methylcyclobutane (C5), dimethylcyclobutane (Ce), and methylcyclopentane (Ce).

[0400] Alkenyl: The term “alkenyl” as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of an unsaturated hydrocarbon compound having one or more carbon-carbon double bonds, which may be aliphatic or alicyclic (cycloalkenyl). The alkenyl group may be a C2-6 or C3-6 alkenyl group.

[0401] Examples of alkenyl groups include, but are not limited to, ethenyl (vinyl, -CH=CH2), 1-propenyl (-CH=CH-CH3), 2-propenyl (allyl, -CH-CH=CH2), isopropenyl (1-methylvinyl, -C(CH3)=CH2), butenyl (C4), pentenyl (C5), and hexenyl (Ce).

[0402] An example of a substituted alkenyl group includes, but is not limited to, styrene (-CH=CHPh or -C(Ph)=CH2).

[0403] Examples of cycloalkenyl groups include, but are not limited to, those derived from cyclopropene (C3), cyclobutene (C4), cyclopentene (C5), cyclohexene (Ce), methylcyclopropene (C4), dimethylcyclopropene (C5), methylcyclobutene (C5), dimethylcyclobutene (Ce), and methylcyclopentene (Ce). Alkynyl: The term “alkynyl” as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of an unsaturated hydrocarbon compound having one or more carbon-carbon triple bonds, which may be aliphatic or alicyclic (cycloalkynyl). The alkynyl group may be a C2-6 or C3-6 alkynyl group.

[0404] Examples of alkynyl groups include, but are not limited to, ethynyl (-C=CH) and 2-propynyl (propargyl, -CH2-C=CH).

[0405] Amino: -NR1R2, wherein R1and R2are independently amino substituents, for example, hydrogen, an alkyl group (also referred to as alkylamino or dialkylamino), an alkenyl group, an alkynyl group, a heterocyclyl group, or an aryl group, preferably H or an alkyl group, or, in the case of a “cyclic” amino group, R1and R2, taken together with the nitrogen atom to which they are attached, form a heterocyclic ring having from 4 to 8 ring atoms. Amino groups may be primary (-NH2), secondary (-NHR1), or tertiary (-NHR1R2), and in cationic form, may be quaternary (-+NR1R2R3). Examples of amino groups include, but are not limited to, -NH2, -NHCH3, -NHC(CH3)2, -N(CH3)2, -N(CH2CH3)2, and -NHPh. Examples of cyclic amino groups include, but are not limited to, aziridino, azetidino, pyrrolidino, piperidino, piperazino, morpholino, and thiomorpholino. The amino group may be -N(R’)2, where each R’ is H or C1-6 alkyl.

[0406] Arylalkyl: The term “arylalkyl” or “aralkyl”, as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of an alkyl group that is covalently bonded to an aromatic ring. The alkyl and aryl part of the group are as defined above. The arylalkyl group may be C6-21, C6-13, Ce-s, or Ce-z arylalkyl group.

[0407] The prefixes (e.g. Ce-2i, C6-13, Ce-s, etc.) denote the number of carbon atoms in the alkyl group and the total number of ring atoms. For example, the term “Cs arylalkyl” as used herein, pertains to an arylalkyl group where the aryl group has 5 or 6 ring atoms and the alkyl chain has 2 or 3 carbon atoms. Typically the alkyl group has 1 or 2 carbon atoms. An example of an arylalkyl group includes, but is not limited to, benzyl (-CH2Ph).

[0408] Alkylaryl: The term “alkylaryl” as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of an aryl group that is covalently bonded to an alkyl group. The alkyl and aryl part of the group are as defined above. The alkylaryl group may be C6-2i, C6-13, C6-s, or C6-z arylalkyl group.

[0409] The prefixes (e.g. Ce-2i, C6-13, Ce-s, etc.) denote the number of carbon atoms in the alkyl group and the total number of ring atoms. For example, the term “Cs alkylaryl” as used herein, pertains to an alkylaryl group where the aryl group has 5 or 6 ring atoms and the alkyl chain has 2 or 3 carbon atoms. Typically the alkyl group has 1 or 2 carbon atoms. An example of an arylalkyl group includes, but is not limited tolyl (-PhMe).

[0410] Aryl: The term “aryl”, as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from an aromatic ring atom of an aromatic compound. The aryl group may be a C5-12, C5-10 or C5-6 aryl group. The aryl group may be based on an aromatic compound which is monocyclic, bicyclic or tricyclic, where the aromatic rings are in aromatic conjunction. The bicyclic and tricyclic aromatic compounds may include fused aromatic rings (e.g., napthyl) or aromatic rings connected by a single covalent bond (e.g., phenyl benzene).

[0411] In this context, the prefixes denote the number of ring atoms, or range of number of ring atoms, whether carbon atoms or heteroatoms. For example, the term “C5-6 aryl” as used herein, pertains to an aryl group having 5 or 6 ring atoms.

[0412] The term aryl may refer to a carboaryl or heteroaryl group. The ring atoms may be all carbon atoms, as in a carboaryl group, such as Ce-io carboaryl. Examples of carboaryl groups include, but are not limited to, phenyl (Ce) and napthyl.

[0413] Alternatively, the ring atoms may include one or more heteroatoms, as in a heteroaryl group, such as C5-12, C5-10 or C5-6 heteroaryl. Examples of monocyclic C5-6 heteroaryl groups include, but are not limited to, those derived from:

[0414] N1: pyrrole (azole) (C5), pyridine (azine) (Ce);

[0415] O1: furan (oxole) (C5);

[0416] Si: thiophene (thiole) (C5);

[0417] N1O1: oxazole (C5), isoxazole (C5), isoxazine (Ce);

[0418] N2O1: oxadiazole (furazan) (C5);

[0419] N3O1: oxatriazole (C5);

[0420] N1S1: thiazole (C5), isothiazole (C5);

[0421] N2: imidazole (1 ,3-diazole) (C5), pyrazole (1 ,2-diazole) (C5), pyridazine (1 ,2-diazine) (Ce), pyrimidine (1 ,3-diazine) (Ce) (e.g., cytosine, thymine, uracil), pyrazine (1 ,4-diazine) (Ce);

[0422] N3: triazole (C5), triazine (Ce); and, N4: tetrazole (C5).

[0423] Ether: -OR, wherein R is an ether substituent, for example, an alkyl group (referred to as alkoxy), an arylalkyl group, an alkenyl group, an alkynyl group, a heterocyclyl group, or an aryl group (referred to as aryloxy), preferably an alkyl group, an arylalkyl group, or an aryl group. Examples of ether groups include, but are not limited to, -OCH3, -OCH2CH3, -O-t-Bu, -OBn, and -OPh. Halo: -F, -Cl, -Br, and -I.

[0424] Haloalkyl group: The term "haloalkyl," as used herein, pertains to an alkyl group, such as an alkyl group described herein, in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with a halogen atom (e.g., F, Cl, Br, I). If more than one hydrogen atom has been replaced with a halogen atom, the halogen atoms may independently be the same or different. Every hydrogen atom may be replaced with a halogen atom, in which case the group may conveniently be referred to as a C perhaloalkyl group. Examples of such groups include, but are not limited to, -CF3, -CHF2, -CH2F, -CCI3, -CBr3, -CH2CH2F, -CH2CHF2, and -CH2CF3.

[0425] Heterocyclyl: The term “heterocyclyl” as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a ring atom of a heterocyclic compound. The heterocyclyl group may be a C3.2o heterocyclyl group of which from 1 to 10 are ring heteroatoms, a C3.z heterocyclyl group of which from 1 to 4 are ring heteroatoms, or a C5-6 heterocyclyl group of which 1 or 2 are ring heteroatoms. In one embodiment, the heterocyclyl group is a C3heterocyclyl group. In one embodiment, the heterocyclyl group is epoxy. In one embodiment, the heterocyclyl group is obtained by removing a hydrogen atom from a ring carbon atom of a heterocyclic compound.

[0426] In one embodiment, the heteroatoms may be selected from O, N or S. In one embodiment the heterocyclyl group is obtained by removing a hydrogen atom from a ring nitrogen atom, where present, of a heterocyclic compound. The heterocyclyl group may be a C3.2o, C3.z, or C5-6 heterocyclyl group.

[0427] In this context, the prefixes (e.g. C3.2o, C3-7, C5-6, etc.) denote the number of ring atoms, or range of number of ring atoms, whether carbon atoms or heteroatoms. For example, the term “Cs-eheterocyclyl”, as used herein, pertains to a heterocyclyl group having 5 or 6 ring atoms.

[0428] Examples of monocyclic heterocyclyl groups include, but are not limited to, those derived from: N1: piperidine (Ce);

[0429] O1: pyran (C6);

[0430] N2: piperazine (Ce);

[0431] O2: dioxane (Ce);

[0432] N1O1: morpholine (Ce);

[0433] Heterocyclyl-alkyl: The term “heterocyclyl-alkyl”, as used herein, pertains to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of alkyl group that is covalently bonded to a heterocyclic compound. The heterocyclic ring or heterocyclyl group is as defined above and may have from 3 to 20 ring atoms, of which from 1 to 10 are ring heteroatoms. Preferably, each ring has from 3 to 7 ring atoms, of which from 1 to 4 are ring heteroatoms.

[0434] In this context, the prefixes (e.g. Ce-z etc.) denote the number of carbon atoms in the alkyl group and the total number of ring atoms, whether carbon atoms or heteroatoms. For example, the term “Ce-z heterocyclyl”, as used herein, pertains to a heterocyclyl group having 5 or 6 ring atoms and an alkyl group having 1 or 2 carbon atoms.

[0435] Siloxane: The term “siloxane”, as used herein, pertains to a monovalent or divalent moiety including at least one Si-0 bond. For example, a monovalent siloxane may include -O-Si(CH3)3, and a divalent siloxane may include -O-Si(CH3)2)-.

[0436] (Alkyl) Aery I ate: The term “(alkyl)acrylate”, as used herein, pertains to a monovalent moiety having the structure CH2=CRC(O)-, where R is a H or an alkyl group.

[0437] Hydroxy: The term “hydroxy”, as used herein, pertains to a monovalent moiety having the structure -OH.

[0438] Other Preferences

[0439] Each and every compatible combination of the embodiments described above is explicitly disclosed herein, as if each and every combination was individually and explicitly recited.

[0440] Various further aspects and embodiments of the present invention will be apparent to those skilled in the art in view of the present disclosure.

[0441] “and / or” where used herein is to be taken as specific disclosure of each of the two specified features or components with or without the other. For example “A and / or B” is to be taken as specific disclosure of each of (i) A, (ii) B and (iii) A and B, just as if each is set out individually herein.

[0442] Unless context dictates otherwise, the descriptions and definitions of the features set out above are not limited to any particular aspect or embodiment of the invention and apply equally to all aspects and embodiments which are described.

[0443] Certain aspects and embodiments of the invention will now be illustrated by way of example and with reference to the figures described above. Examples

[0444] Measurement Methods

[0445] Analytical methods for assessing properties of rigid gas permeable materials and ophthalmic lenses are described below:

[0446] Mechanical Properties

[0447] Flexural mechanical data is obtained following the method described in ANSI Z80.20 for Ophthalmics -Contact Lenses - Standard Terminology, Tolerances, Measurements and Physicochemical Properties, Section 7.13 Flexural Strength and Section 7.16 Modulus of Elasticity. The test specimen is lathed from a cylinder of 12.7mm diameter and to a thickness of 0.50mm. The specimen is placed centrally on a test holder configured as described in the above standard. The test is then conducted using a 3-point bend program run on a Zwick Z0.5 mechanical testing instrument equipped with an Xforce HP 500N load cell. The crosshead speed of the instrument is 0.213 mm / min and the data collected as a graphical plot of stress vs. strain. Flexural strength is equal to the maximum stress in the outer fibres at the moment of break. Flexural strength can be calculated from the formula: ofm = 3PL / 2bd2

[0448] Where: OFM: flexural strength, Mpa, P: maximum load on the load-deflection curve, equivalent here to ofMax, N, L: support span, mm, b: width of beam tested, mm, d: depth of beam tested, mm.

[0449] The modulus of elasticity is described (according to ANSI Z80.20) as the tangent to the straight- line portion of the load-deflection curve at small deflections: It can be described as:

[0450] Ef = (stress @ 3%strain)-(stress @ 1 % strain) (strain @ 3% strain)-(strain @ 1 % strain)

[0451] Where: Ef= Tangent Modulus of Elasticity

[0452] The unit of the flexural modulus is MPa (megapascal).

[0453] Oxygen Permeability

[0454] Oxygen permeability is measured in a high humidity environment at 35° C. The oxygen permeability is measured using the procedure outlined in the following standard. ISO 18369- 4:2006 Ophthalmic Optics — Contact lenses — Part 4: Physicochemical properties of contact lens materials. This corresponds to section 4.4 Oxygen Permeability and more specifically section 4.4.3 Polarographic method. Measurements were made using an 02 Permeometer Model 201 T supplied by the Rehder Development Company, California, USA.

[0455] For each material to be measured a minimum of 4 piano contact lenses with different centre thicknesses (t) ranging from 0.10 to 0.30 mm are prepared following normal lens manufacturing methods. Designs of the lenses are such that their central regions, from where oxygen flux measurements are taken, are of constant thickness. For each lens an initial oxygen transmissibility (Dk / t) measurement is determined, and then corrected for edge effects by application of a numerical method described in ISO 18369-2017. To correct for boundary effects, the reciprocal of the corrected oxygen transmissibilities of each of the lenses is plotted against t. The inverse of the gradient of the least squares best fit of the line is equal to the corrected Oxygen Permeability (Dk) of the material. Plano is a lens with zero power and as such does not provide any visual correction. Dk measurements are performed on piano lenses because the front and back surfaces are parallel to each other. Consequently, the lens is of constant thickness over the area the measurement is being taken from.

[0456] As described by ISO 18369-2017 the equipment is calibrated using reference materials obtained from the Oxygen Permeability Reference Material Repository at the University of Alabama, Birmingham, USA. The corrected Dk of 4 reference materials with Oxygen Permeability in the range of 20-116 Barrers are determined by the method described above, and then used to construct a calibration curve from which a linear regression is derived. The calibrated and corrected Dk of an unknown sample can then be derived by application of the linear regression to the corrected Dk initially measured. The unit of oxygen permeability (Dk) is Barrers.

[0457] Shore D Hardness

[0458] Shore D Hardness is measured using a calibrated Shore Scale Durometer Hardness Tester supplied by Bowers Metrology, UK and following ASTM D2240. A 12.7x5mm trimmed blank of material is placed in line with the needle on the durometer. The blank is moved up as quickly as possible without shock towards the needle on the durometer, raising the weight until the needle on the dial will not move any further. The handle is held in this position for one second and the readings recorded. Two measurements can be taken from the durometer, impact and rest shore D values. Impact shore D is the initial contact between the indenting foot and the material. The rest shore D value is when there is high resistance between the foot and material and indentation stops. Shore D Hardness is a unitless parameter.

[0459] Sessile Drop Contact Angle Sessile drop contact angle is determined using the sessile drop technique using the Kriiss Easy Drop Shape Analysis System. A fluorinated rigid gas permeable lens to be measured is placed on a dome support, if the lens has been stored in saline the front surface is lightly blotted dry with a lint free tissue. A 2.0 pL drop of distilled water is placed on the surface of the material being measured, and a digital image of the drop captured. The sessile contact angle is then measured from the image and is the angle that the drop of water makes with the surface. The angle at both sides of the drop is measured and averaged. The lens is initially measured in the dry state, and then again after 7 days of storage in borate buffered saline. The unit of sessile drop contact angle is degrees (°).

[0460] Refractive Index

[0461] Refractive index is measured using the procedure outlined in ISO 18369-4 Ophthalmic Optics - Contact Lenses. Part 4 - Physicochemical Properties Section 4.5 Refractive index. Refractive index is determined by measuring the critical angle of incidence for total internal reflection of light using a calibrated Bellingham & Stanley Benchtop Refractometer Abbe refractometer at 20°C and a wavelength of 589nm. Test samples are prepared by lathing buttons to a flat disc, so that they can be flattened against the reference surface of the refractometer. The test surfaces of the discs are finished to a quality acceptable in normal contact lens production. The test disc is pressed firmly against the refractometer fixed prism with 1 -Bromonaphthalene contact fluid. The material’s refractive index is then read from the instrument’s eyepiece. The refractive index is a unitless parameter.

[0462] Crosslinker Synthesis

[0463] The following crosslinker was prepared (Crosslinker 1). The reactants described herein were obtained from commercial sources or prepared using suitable methods known to those skilled in the art.

[0464] Crosslinker 1 ([2,3,5,6-Tetrafluoro-4-(2-methylprop-2-enoyloxymethyl)phenyl]methyl 2- methylprop-2-enoate / Tetrafluorobenzyl di meth acrylate)

[0465] Crosslinker 1 Tetrafluorobenzene dimethanol (15.0g, 71.31 mmol) was placed in a 100ml three-neck reaction flask. Toluene (40g, 434mmol) was added, followed by dropwise addition of methacrylic anhydride (23.11g, 149.91 mmol, 2.1 equivalent) while stirring. An off-white suspension was obtained. Concentrated sulphuric acid (0.297g, 3.0mmol, 0.04 equivalent) was slowly added to the reaction flask, causing a slight exotherm. After stirring for 16 hrs at room temperature, a clear solution with a light peach tint was obtained. The GC-MS analysis indicates that 93% of the desired product was obtained. The reaction mixture was neutralised with aqueous sodium bicarbonate solution and extracted with toluene. The aqueous layer was washed with toluene. The combined organic layer was dried over magnesium sulphate and then filtered. The solvent was evaporated, and the product, tetrafluorobenzyl dimethacrylate (Crosslinker 1), was further purified by recrystallization (16g, 99.97% GC).

[0466] Fluorosilicone Polymer Synthesis

[0467] The following inventive polymers were prepared (Examples 1 to 23). The composition and polymerization conditions are specified in Table 1. The reactants described herein were obtained from commercial sources or prepared using suitable methods known to those skilled in the art.

[0468] Example 1 (Pn319D002A)

[0469] A fluorosilicone polymer was prepared through polymerisation of a composition as follows: Hexafluoroisopropyl methacrylate (31.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%) t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). The reaction mixture was thoroughly mixed and subsequently dispensed into cylindrical molds which were sealed and placed in a water bath at approximately 60°C for approximately 48 h, then at approximately 70°C for approximately 8 h.. The resulting polymer is removed from the molds and annealed by heating in a vacuum oven for at least 48 h at a temperature of approximately 110°C. This material has a Dk of 230.0 Barrers

[0470] Example 2 (Pn319D002B)

[0471] The same procedure was followed as example 1 but the following polymerisable composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), Pentafluorophenyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 123.6 Barrers.

[0472] Example 3 (Pn319D002C)

[0473] The same procedure was followed as example 1 but the following polymerisable composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), Pentafluorobenzyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 133.0 Barrers

[0474] Example 4 (Pn319D002E)

[0475] The same procedure was followed as example 1 but the following polymerisable composition was used: Hexafluoroisopropyl methacrylate (47.5 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3- [(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 160.4 Barrers.

[0476] Example 5 (Pn319D002F)

[0477] The same procedure was followed as example 1 but the following polymerisable composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), Pentafluorophenyl methacrylate (47.5 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 68.6 Barrers.

[0478] Example 6 (Pn319D003B)

[0479] The same procedure was followed as example 1 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), Pentafluorostyrene (31.0 wt. %), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 154.1 Barrers. Example 7 (Pn319D003C)

[0480] The same procedure was followed as example 1 but the following polymerisation composition was used: Hexafluoroisopropyl methacrylate (47.5 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3- [(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 173.7 Barrers.

[0481] Example 8 (Pn319D003D)

[0482] The same procedure was followed as example 1 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), Pentafluorostyrene (47.5 wt. %), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 102.3 Barrers.

[0483] Example 9 (Pn319D004B)

[0484] The same procedure was followed as example 1 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), Difluoroethyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 94.7 Barrers.

[0485] Example 10 (Pn319D004C)

[0486] The same procedure was followed as example 1 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), Pentafluorobenzyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 119.9 Barrers.

[0487] Example 11 (Pn319D005B)

[0488] The same procedure was followed as example 1 but the following polymerisation composition was used: Hexafluoroisopropyl methacrylate (31.0 wt.%), 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) (55.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 119.3 Barrers.

[0489] Example 12 (Pn319D005C)

[0490] The same procedure was followed as followed as example 1 but the following polymerisation composition was used: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) (55.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), Difluoroethyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 66.9 Barrers.

[0491] Example 13 (Pn319D005D)

[0492] The same procedure was followed as followed as example 1 but the following polymerisation composition was used: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) (55.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), Pentafluorophenyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 82.5 Barrers.

[0493] Example 14 (Pn319D005E)

[0494] The same procedure was followed as followed as example 1 but the following polymerisation composition was used: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) (55.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), Pentafluorobenzyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 78.6 Barrers.

[0495] Example 15 (Pn319D005F)

[0496] The same procedure was followed as followed as example 1 but the following polymerisation composition was used: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) (55.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), Pentafluorostyrene (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 113.5 Barrers.

[0497] Example 16 (Pn319D006A)

[0498] The same procedure was followed as example 1 but the cylindrical molds were sealed and placed in a water bath at approximately 60°C for approximately 20 h then at approximately 70°C for approximately 8 h, and the following polymerisable composition was used: Hexafluoroisopropyl methacrylate (31.0 wt.%), Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 249.4 Barrers.

[0499] Example 17 (Pn319D006B)

[0500] The same procedure was as example 16 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), 2, 2,3,3- Tetrafluoropropyl methacrylate (31.0 wt%.), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%),t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 145.3 Barrers.

[0501] Example 18 (Pn319D006C)

[0502] The same procedure was as example 16 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (2.0 wt%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), Trifluoroethyl methacrylate (31.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 153.3 Barrers.

[0503] Example 19 (Pn319D006G)

[0504] The same procedure was as example 16 but the following polymerisation composition was used: Hexafluoroisopropyl methacrylate (45.5 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), N- Vinyl pyrrolidone (2.0 wt.%), p-Vinylbenzyl methacrylate (2.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%),t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 163.5 Barrers.

[0505] Example 20 (Pn319D006H)

[0506] The same procedure was as example 16 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (6.0 wt%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), N-Vinyl pyrrolidone (2.0 wt.%), 2,2,3,3-Tetrafluoropropyl methacrylate (45.5 wt%.), p-Vinylbenzyl methacrylate (2.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’- azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 58.8 Barrers.

[0507] Example 21 (Pn319D006l)

[0508] The same procedure was as example 16 but the following polymerisation composition was used: Methacrylic acid (6.0 wt.%), Ethylene glycol dimethacrylate (6.0 wt%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), N-Vinyl pyrrolidone (2.0 wt.%), 2,2,3,3-Tetrafluoropropyl methacrylate (45.5 wt%.), p-Vinylbenzyl methacrylate (2.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’- azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 88.5 Barrers.

[0509] Example 22 (Pn319D020B)

[0510] The same procedure was followed as example 1 but the following polymerisation composition was used: Hexafluoroisopropyl methacrylate (31.0 wt.%), Methacrylic acid (6.0 wt.%), [2, 3,5,6- Tetrafluoro-4-(2-methylprop-2-enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate (Crosslinker 1) (8.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’- azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 262.2 Barrers.

[0511] Example 23 (Pn319D020D)

[0512] The same procedure was followed as example 1 but the following polymerisation composition was used: Pentafluorostyrene (31.0 wt.%), Methacrylic acid (6.0 wt.%), [2,3,5,6-Tetrafluoro-4- (2-methylprop-2-enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate (Crosslinker 1) (8.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 173.9 Barrers. Table 1 A and 1 B summarise the details of the formulations of the polymer compositions detailed in examples 1 to 23 together with the polymerisation conditions used to obtain the polymer compositions.

[0513] Table 1A - Summary of Composition and Polymerisation Conditions of Examples 1-10

[0514] Table 1B - Summary of Composition and Polymerisation Conditions of Examples 11-23

[0515] The following comparative polymers were prepared (Comparative Examples 1 to 6). The composition and polymerization conditions are provided in Table 2.

[0516] Comparative Example 1 (Pn305D037A)

[0517] A comparative polymer was prepared through polymerisation of a composition as follows: Methacrylic acid (6.0 wt%), Methyl methacrylate (36.0 wt.%), 3-(4-ethenylphenyl)-1 , 1 ,1 , 5,5,5- hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (50 wt.%), p-Vinylbenzyl methacrylate (8.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). The reaction mixture was thoroughly mixed and subsequently dispensed into cylindrical molds which were sealed and placed in a water bath at approximately 60°C for approximately 20 h, then at approximately 70°C for approximately 8 h. The resulting polymer is removed from the molds and annealed by heating in a vacuum oven for at least 48 h at a temperature of approximately 110°C. This material has a Dk of 52.6 Barrers.

[0518] Comparative Example 2 (Pn305D037D)

[0519] The same procedure was followed as comparative example 1 but the following polymerizable composition was used: Methacrylic acid (6.0 wt.%), 2- Hydroxyethyl methacrylate (13.0 wt.%), Methyl methacrylate (5.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3- [(trimethylsilyl)oxy] (Styryl TRIS) (60.0 wt.%), N-Vinyl pyrrolidone (8.0 wt.%), p-Vinylbenzyl methacrylate (8.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’- azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4- methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 70.8 Barrers.

[0520] Comparative Example 3 (Pn319D001A)

[0521] The same procedure was followed as comparative example 1 but the following polymerizable composition was used: Methacrylic acid (6.0 wt.%), Methyl methacrylate (38.0 wt.%), 3-(4- ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (50.0 wt.%), p- Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4- bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 43.9 Barrers.

[0522] Comparative Example 4 (Pn319D002D)

[0523] The same procedure was followed as comparative example 1 but the cylindrical molds were sealed and placed in a water bath at approximately 60°C for approximately 88 h , then at approximately 70°C for approximately 4 h, and the following polymerizable composition was used: Methacrylic acid (6.0 wt.%), Methyl methacrylate (31.0 wt.%) , Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS) (55.0 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3- hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t- butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 63.4 Barrers.

[0524] Comparative Example 5 (Pn319D002G)

[0525] The same procedure was followed as comparative example 4 but the following polymerizable composition was used: Methacrylic acid (6.0 wt.%), Methyl methacrylate (47.5 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3- [(trimethylsilyl)oxy] (Styryl TRIS) (38.5 wt.%), p-Vinylbenzyl methacrylate (6.0 wt.%), 2-(4- Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4-bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 21.3 Barrers.

[0526] Comparative Example 6 (Pn319D005G)

[0527] The same procedure was followed as comparative example 1 but the cylindrical molds were sealed and placed in a water bath at approximately 60°C for approximately 48 h, then at approximately 70°C for approximately 8 h, and the following 77olymerizable composition was used: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) (55.0 wt.%), Methacrylic acid (6.0 wt.%), Methyl methacrylate (31 .0 wt.%), Ethylene glycol dimethacrylate (2.0 wt.%), p- Vinylbenzyl methacrylate (6.0 wt.%), 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (0.5 wt.%), 2,2’-azobisisobutyronitrile (AIBN) (0.100 wt.%), t-butyl peroxybenzoate (0.200 wt.%) and 1 ,4- bis(4-methylanilino)anthracene-9, 10-dione (Solvent Green 3) (0.0075 wt.%). This material has a Dk of 43.7 Barrers.

[0528] Table 2 summarises the details of the formulations of the polymer compositions detailed in Comparative Examples 1 to 6 together with the polymerisation conditions used to obtain the polymer compositions.

[0529] Table 2 - Summary of Composition and Polymerisation Conditions of Comparative Examples 1-6 The properties of the Example polymers were tested. For Inventive Examples 1 to 21 and Comparative Examples 1 to 6, the oxygen permeability (Dk), Refractive Index (measured at 20°C and a wavelength of 589nm), Hardness (impact), Hardness (rest), Sessile Contact - Initial, Sessile Contact angle - after 1 week and Flexural Modulus were all measured. The measurement methods are as described above.

[0530] The results of the tests are shown in Table 3.

[0531] Table 3 - Summary of Physical Properties of Polymer Compositions

[0532] As seen in Table 3, the examples of the invention generally achieve higher values for oxygen permeability when compared to the comparative examples. The absence of a fluorinated monomer within the polymerizable composition generally results in a low oxygen permeability of the resulting polymer. For example, comparative examples 1 , 3, 5 and 6 demonstrate an oxygen permeability of below 55 Barrers.

[0533] The inventive examples all demonstrate an oxygen permeability of above 55 Barrers, as seen in Table 3. Examples 1 , 4, 7, 11 and 16 which contained PFAS monomers demonstrated high oxygen permeabilities of 230.0, 160.4, 173.7, 119.3 and 249.4 Barrers respectively.

[0534] Furthermore, all inventive examples demonstrate a suitable refractive index for used in an ophthalmic lens.

[0535] Inventive examples containing non-PFAS fluorinated monomers pentafluorobenzyl methacrylate, pentafluorophenyl methacrylate, pentafluorostyrene, difluoroethyl methacrylate and 2,2,3,3-tetrafluoropropyl methacrylate also demonstrated good oxygen permeability comparable to Examples containing PFAS monomers. For example, inventive examples 2, 3, 6, 8, W and 15 demonstrated good oxygen permeabilities of 123.6, 133.0, 154.1 , 102.3, 119.9 and 113.5 Barrers, respectively. This demonstrates that when combined with a second polymerizable component as defined within the invention, fluorinated non-PFAS monomers as defined in the invention may achieve comparable oxygen permeabilities to those obtained through the use of PFAS monomers.

[0536] In general, the use of styryl TRIS as the second polymerizable component resulted in polymers demonstrating high oxygen permeability. Without wishing to be bound by theory, the presence of an aryl group on the second polymerizable component may result in improved oxygen permeability in both PFAS and fluorinated non-PFAS monomers.

[0537] Additionally, inventive examples containing [2,3,5,6-Tetrafluoro-4-(2-methylprop-2- enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate (i.e., Crosslinker 1) as a crosslinking fourth polymerizable component resulted in polymers demonstrating high oxygen permeability for both PFAS and non-PFAS containing examples. For example, PFAS-containing inventive example 22 and non-PFAS-containing inventive example 23 demonstrated good oxygen permeabilities of 262.2 and 173.9 Barrers, respectively. This demonstrates that when combined with a fourth polymerizable component as defined in the invention, and in particular, when combined with the crosslinker [2,3,5,6-Tetrafluoro-4-(2-methylprop-2- enoyloxymethyl)phenyl]methyl 2-methylprop-2-enoate, fluorinated non-PFAS monomers as defined in the invention may achieve comparable oxygen permeabilities to those obtained through the use of PFAS monomers. Table 4A and 4B summaries the details of the formulations of comparative example 4 and inventive examples 1 , 2, 3, 6, 9, 10, 16, 17 and 18.

[0538] Table 4A - Composition of Comparative Example 4 and Inventive Examples 1, 2, 3, 6, 9 and 10 Table 4B - Composition of Comparative Example 4 and Inventive Examples 16, 17 and 18

[0539] Comparison of the oxygen permeability (Dk), Refractive Index (measured at 20°C and a wavelength of 589nm), Hardness (impact), Hardness (rest), Sessile Contact - Initial, Sessile Contact angle - after 1 week and Flexural Modulus, for comparative example 4 and closely related inventive examples 1 , 2, 3, 6, 9, 10, 16, 17 and 18 are shown in Table 5 below.

[0540] Table 5 - Physical Properties of Comparative Polymer Composition 4 and Inventive Polymer Compositions 1, 2, 3, 6, 9, 10, 16, 17 and 18 As seen Table 5, inventive examples 1 , 2, and 3 where the formulation and the polymerisation conditions were identical to that of comparative example 4, apart from presence of the inventive fluorinated monomer, higher oxygen permeability was demonstrated.

[0541] Inventive examples 7, 9, 10, 16, 17 and 18 additionally underwent different reaction times to that of comparative example 11 . Greater oxygen permeability was also demonstrated in these inventive examples.

[0542] Table 6 summaries the details of the formulations of the comparative example 5 and inventive examples 4, 5, 7 and 8.

[0543] Table 6 - Composition of Comparative Example 5 and Inventive Examples 4, 5, 7 and 8

[0544] Comparison of the oxygen permeability (Dk), Refractive Index (measured at 20°C and a wavelength of 589nm), Hardness (impact), Hardness (rest), Sessile Contact - Initial, Sessile Contact angle - after 1 week and Flexural Modulus, for comparative example 5 and closely related inventive examples 4, 5, 7 and 8 are shown in Table 7 below.

[0545] Table 7 - Physical Properties of Comparative Polymer Composition 5 and Inventive Polymer Compositions 4, 5, 7 and 8 As seen Table 7, inventive examples 4 and 5 where the formulation and the polymerisation conditions were identical to that of comparative example 5, apart from presence of the fluorinated monomer, higher oxygen permeability was demonstrated. Inventive examples 7 and 8 additionally underwent different reaction times to that of comparative example 5. Greater oxygen permeability was also demonstrated in these inventive examples.

[0546] Table 8 summaries the details of the formulations of the comparative example 6 and inventive examples 11-15.

[0547] Table 8 - Composition of Comparative Example 6 and Inventive Examples 11-15

[0548] Comparison of the oxygen permeability (Dk), Refractive Index (measured at 20°C and a wavelength of 589nm), Hardness (impact), Hardness (rest), Sessile Contact - Initial, Sessile Contact angle - after 1 week and Flexural Modulus, for comparative example 6 and inventive examples 11-15 are shown in Table 9 below. Table 9 - Physical Properties of Comparative Polymer Composition 6 and Inventive Polymer Compositions 11-15 As seen Table 9, inventive examples 11-15 where the formulation and the polymerisation conditions were identical to that of comparative example 6, apart from presence of the fluorinated monomer, higher oxygen permeability was demonstrated.

[0549] Thus, Tables 5, 7 and 9, indicate that the invention is effective with use of PFAS and non-PFAS fluorinated non-PFAS monomers, across a broad range of polymerisation conditions, polymerisable monomers / components and their individual quantities.

Claims

Claims:1 . An ophthalmic lens comprising a polymer obtained from curing a polymerizable composition comprising: a first polymerizable monomer having an alkenyl group and at least one fluoro group; and a second polymerizable component selected from a polymerizable monomer having an alkenyl group and at least one siloxane group, and a polymerizable pre-polymer having an alkenyl group and at least one siloxane group.

2. The ophthalmic lens of claim 1 , wherein the first polymerizable monomer comprises: a) an (alkyl)acrylate group comprising the alkenyl group, wherein the one or more fluoro groups are provided within a moiety connected to the alcoholic portion of the (alkyl)acrylate group; or b) a substituted aryl group connected directly to the alkenyl group, wherein the aryl group is substituted with the one or more fluoro groups.

3. The ophthalmic lens of claim 1 or 2, with the proviso that: the first polymerizable monomer does not contain a trifluoromethyl group connected to a carbon atom, preferably the first polymerizable monomer does not contain a trifluoromethyl group; and / or the first polymerizable monomer does not contain two or more adjacent diflouromethylene groups, preferably the first polymerizable monomer does not contain a difluoromethylene group.

4. The ophthalmic lens of any one of claims 1 to 3, wherein the first polymerizable monomer has the general formula (I):R4R3YLRR21wherein:-R1, -R2and -R3are each independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R1is methyl, -R2is -H, and R3is -H;-L1- is selected from a covalent bond,, anwhere the asterisk * indicates the point of connection to -R4;-R4is selected from substituted C6-12 aryl, substituted C1-10 alkyl and substituted C2-C10 heteroalkyl, and the aryl, alkyl and heteroalkyl groups are substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halo substituents selected from chloro, iodo and bromo; and where -R4is substituted Ce-io aryl then -R5- is C1-10 alkylene or C2-C10 heteroalkylene, and where -R4is substituted C1-10 alkyl or substituted C2-C10 heteroalkyl then -R5- is a covalent bond.

5. The ophthalmic lens of claim 4, wherein:-R4is phenyl, naphthyl, or phenylbenzene, preferably phenyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent, and optionally further substituted, such as optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo, or one or more groups containing halos substituents selected from chloro, iodo and bromo, and-R5- is C1-10 alkylene or C2-C10 heteroalkylene.

6. The ophthalmic lens of claim 5, wherein -R4is pentafluorophenyl, and -R5- is C1-10 alkylene or C2-C10 heteroalkylene.

7. The ophthalmic lens of claim 6, wherein -R4is pentafluorophenyl, and -R5- is methylene.

8. The ophthalmic lens of claim 4, wherein -R4is substituted C1-10 alkyl or substituted C2- C10 heteroalkyl, substituted with the at least one fluoro substituent or at least one group containing a fluoro substituent and is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halos substituents selected from chloro, iodo and bromo, and -R5- is a covalent bond.

9. The ophthalmic lens of claim 8, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of the following: -F, -CF3, -CF2H, -CF2CI, -CFCh, and mixtures thereof, wherein -R4is optionally further substituted with one or more halo substituents selected from choro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CC , -CCI2H, -CBr3, -CBr2H, -Cl3, -CI2H, and mixtures thereof.

10. The ophthalmic lens of claim 9, wherein the at least one fluoro substituent or at least one group containing a fluoro substituent of -R4is selected from one or more of: -F, -CF3, -CFH2, - CF2H, -CF2CI, -CFCI2, and mixtures thereof,and where -R4is -CF3then -L1- is where the asterisk * indicates the point of connection to -R4, and wherein -R4is optionally further substituted with one or more halo substituents selected from chloro, iodo and bromo or one or more groups containing halo substituents selected from one or more of the following: -CCI3, -CCI2H, -CBr3, -CBr2H, -Cl3, -CI2H, and mixtures thereof.11 . The ophthalmic lens of claims 8 or 9, wherein -R4is selected from one of the following:

12. The ophthalmic lens of any one of claims 8 to 10, wherein -R4is selected from one of the following:where the asterisk * indicates the point of connection to -R4.

13. The ophthalmic lens of any one of claims 1 to 12, wherein the second polymerizable component having an alkenyl group and at least one siloxane group has the general formula (II):wherein:-R6, -R7, and -R8are independently selected from -H and C1-4 alkyl, preferably -H and methyl, more preferably -R6is methyl, -R7is -H, and -R8is -H;-L2- is selected from a covalent bond,wherein the asterisk * indicates the point of connection to -R9-;-R9- is selected from optionally substituted Ce-io arylene, optionally substituted C1-10 alkylene and optionally substituted C2-10 heteroalkylene; where -R9- is optionally substituted Ce-io arylene then -R11- is optionally substituted C1-10 alkylene, optionally substituted C2-10 heteroalkylene, or a covalent bond, and where -R9- is optionally substituted C1-10 alkylene or optionally substituted C2-10 heteroalkylene then -R11- is a covalent bond; and-R10is -Si(OSi(R12)3)3, -Si(OSi(R12)3)2Ri2, -Si(O[Si(R12)2O]rRi2)2R12, or -Si(O[Si(R12)2O]rRi2)3where each -R12is independently selected from C1-10 alkyl and -OH, and r is 2 to 25.

14. The ophthalmic lens of claim 13, wherein -R9- is arylene, such as phenylene, such as phenyl-1 , 4-ene.

15. The ophthalmic lens of claim 13 or 14, wherein the second polymerizable component is a polymerizable monomer, wherein -R10is -Si(OSi(R12)3)3or -Si(OSi(R12)3)2Ri2.

16. The ophthalmic lens of any one of claims 13 to 15, wherein the second polymerizable component having an alkenyl group and at least one siloxane group is selected from trisiloxane, 3-(4-ethenylphenyl)-1 ,1 ,1 ,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy] (Styryl TRIS), 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS), tris(trimethylsilyloxy)-[2-(4- vinylphenyl)ethyl]silane (Styrylethyl TRIS), [2-hydroxy-3-[3-[methyl- bis(trimethylsilyloxy)silyl]propoxy]propyl] prop-2-enoate (SIGMA), methacryloxypropylbis(trimethylsiloxy)silanol and mixtures thereof.

17. The ophthalmic lens of any one of claims 13 to 14, wherein the second polymerizable component is the polymerizable pre-polymer having an alkenyl group and at least one siloxane group, wherein -R10is -Si(O[SI(R12)2O]rRi2)2R12or -Si(O[SI(R12)2O]rRi2)3.

18. The ophthalmic lens of claim 17, wherein the polymerizable pre-polymer is selected from monomethacrylated polydimethylsiloxane, monomethacryloxypropyl terminated polydimethylsiloxane, methacryloxypropyl T-structure siloxane, and mixtures thereof.

19. The ophthalmic lens of any one of claims 1 to 18, wherein: the amount of first polymerizable monomer is present in the composition in an amount from 10 to 75 wt.% based on the total weight of the composition; and the second polymerizable component is present in the composition in an amount from 10 to 75 wt.% based on the total weight of the composition.

20. The ophthalmic lens of any one of claims 1 to 19, wherein the polymerizable composition further comprises a third polymerizable monomer for copolymerization with the first polymerizable monomer and the second polymerizable component, wherein the third monomer has at least one alkenyl group and differs from each of the first polymerizable monomer and second polymerizable component, and optionally the polymerizable composition further comprises a fourth polymerizable component for forming crosslinks with the polymerizablemonomers and the second polymerizable component in the polymerizable composition, wherein the fourth polymerizable monomer is selected from a polymerizable monomer having at least two alkenyl groups, and a polymerizable pre-polymer having at least two alkenyl groups.21 . The ophthalmic lens of claim 20, wherein the third and / or fourth polymerizable monomer comprises at least one substituted arylene group having at least one fluoro substituent or fluorocontaining substituent group.

22. The ophthalmic lens of claim 20 or 21 , wherein the fourth polymerizable monomer is selected from one or more of:wherein preferably the fourth polymerizable monomer is selected from one of more of:wherein more preferably, the fourth polymerizable monomer is selected from one of more of:

23. The ophthalmic lens according to any one of claims 1 to 22, wherein the ophthalmic lens is a contact lens or an intraocular lens, preferably a contact lens.

24. A polymerizable composition, as described in any one of claims 1 to 22.

25. An optical material comprising a polymer obtained or obtainable from curing a polymerizable composition of claim 24.

26. A method of forming an optical material, comprising curing a polymerizable composition of claim 24, and optionally annealing the resulting cured material.

27. A method of forming an ophthalmic lens of any one of claims 1 to 23, wherein the method comprises the steps of:I) curing the polymerizable composition of claim 24 in a mould to form a molded product;II) optionally annealing the moulded product; and ill) working the molded product to form an ophthalmic lens.

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