Hyper gas permeable materials for ophthalmic applications

Abstract

In one aspect, the present disclosure relates to ophthalmic devices comprising a hyper gas-permeable material. The present disclosure further relates to hyper gas-permeable polymers, materials, products comprising the polymers or materials, and methods of making thereof. In one aspect, the instant disclosure provides polymer materials that have required Dk number while not requiring PFAS component. In one aspect, the polymer materials provides oxygen permeability by, in part, increasing gas diffusivity. In some embodiments, the polymer materials comprise percolated channels.

Description

HYPER GAS PERMEABLE MATERIALS FOR OPHTHALMIC APPLICATIONSBACKGROUND

[0001] Making hyper oxygen permeable (ultra-high Dk) materials without using PFAS (perfluoro alkyl substances) is a serious challenge for the design of ophthalmic devices, where PFAS is widely used for oxygen permeability enhancement. In current industry, replacing PFAS with other chemical structures leads to a considerable drop in Dk numbers.

[0002] Reaching high Dk without using PFAS has been a significant challenge in the ophthalmic industry for decades. As of now, high-Dk rigid gas permeable (RGP) contact lenses are produced of perfluoroalkyl substances polymers that lead to serious environmental and health risks associated with the so-called forever chemicals composed of PFAS. The use of PFAS has been necessitated by having high oxygen permeability for healthy condition for cornea. Patients wearing lenses with low Dk complain of eye strain, fatigue, irritation and cornea inflammation due to insufficient oxygen supply to the cornea. While current RGP and scleral contact lenses afford some degree of oxygen permeability (Dk values of 30-70 for PFAS-free lenses and up to 140-145 for PFAS-containing lenses), patients continue to report (suffer from) eye fatigue and eye strain as the day progresses. Since the wear time has increased based on unmet market needs, fatigue and strain due to the insufficient oxygen supply to the cornea become serious issues. There is an urgent need in a PFAS-free material suitable for use as a RGP and scleral lens which exhibits ultra-high oxygen permeability with Dk number higher than 145.

[0003] The cornea needs oxygen to stay alive, healthy, and transparent, which is necessary for focusing light. The cornea doesn't have blood vessels, so it relies on oxygen supply from the surrounding air and the tears that coat the eye. Several acute health symptoms may happen if the cornea does not get enough oxygen. 1) Swelling: The cornea will swell due to a buildup of lactic acid, which pulls water into the cornea. 2) Clouding: The cornea can become cloudy after period of lack of oxygen. 3) Vision loss: New blood vessels can grow in the cornea, which can leak and lead to vision loss. 4) Contact lens intolerance: The cornea may become intolerant to contact lenses.

[0004] Human corneal heath relies on avascular oxygen supply. Under normal conditions, oxygenation of the anterior cornea is achieved by exposure to the atmosphere when the eye is open, and by exposure to the palpebral conjunctiva when the eye is closed. Upon eye closure, corneal oxygenation is reduced because the palpebral conjunctiva has roughly one-third of the atmospheric concentration. Low-oxygen-transmissible RGP contact lenses (RGP and Scleral) further impede oxygen flow to the cornea with possible loss of corneal transparency upon overwear. In exceptional cases, keratitis, microcysts, and acidosis can result. Consequently, the role of RGP and scleral oxygen permeability (=Dk, where D is the diffusion coefficient and k is the partition coefficient of oxygen in the lens material) in corneal hypoxia has been extensively studied. To assess the critical oxygen requirement, all prior art efforts have considered the molecular diffusion of oxygen into the cornea, accounting for its reactive loss within the corneal tissue.

[0005] Therefore, there is a significant demand in reducing reliance on PFAS materials and developing new materials that possess required Dk numbers.SUMMARY

[0006] In one aspect, disclosed herein is a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising: (a) one or more high Tgcross linkers; (b) one or more high Tgmonomers; and (c) one or more siloxane-containing monomers, wherein the siloxane-containing polymer has a Dk number of at least 45. In one aspect, disclosed herein is a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising: (a) one or more high Tgcross linkers; (b) one or more high Tgmonomers; and (c) one or more siloxane-containing monomers; wherein the siloxane-containing polymer comprises a percolation structure. In some embodiments, the percolation structure exceeds a percolation threshold. In some embodiments, the microphase separation generates domains in the polymer structure that they percolate and make channels for better permeability to oxygen. In one aspect, disclosed herein is a material for ophthalmic device comprising a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising: (a) one or more high Tgcross linkers; (b) one or more high Tgmonomers; and (c) one or more siloxane-containing monomers; wherein the siloxane-containing polymer has a Dk number of at least 45. In some embodiments, the siloxane-containing polymer comprises a percolation structure. In some embodiments, the percolation structure exceeds a percolation threshold. In one aspect, disclosed herein is a material for ophthalmic device comprising a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising: (a) one or more high Tgcross linkers; (b) one or more high Tgmonomers; and (c) one or more siloxane-containing monomers; wherein the siloxane-containing polymer comprises a percolation structure. In some embodiments, the percolation structure exceeds a percolation threshold. In some embodiments, the siloxane-containing polymer is substantially free of PFAS material. In some embodiments, the percolation structure are percolated channels. In some embodiments, the percolated channels are formed upon microphase separation of the siloxane-containing polymer.

[0007] In some embodiments, the percolation threshold is sufficient to allow the permeation of oxygen. In certain embodiments, the siloxane-containing polymer comprises a percolation structure. In certain embodiments, the percolation structure exceeds a percolation threshold. In certain embodiments, the siloxane-containing polymer is substantially free of PFAS material. In certain embodiments, the percolation structure are percolated channels. In certain embodiments, the percolated channels of siloxane-rich material (component) are formed upon microphase separation of the siloxane-containing polymer. In certain embodiments, the percolated channels are formed upon microphase separation of the siloxane-containing polymer. In certain embodiments, exceeding the percolation threshold significantly facilitates the permeation (transmission) of oxygen through an optical device material. In certain embodiments, the percolation threshold is sufficient to allow the permeation of oxygen. In certain embodiments, the one or more siloxane-containing monomers comprise one or more bulky siloxane monomers. In certain embodiments, the one or more bulky siloxane monomers comprise Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane, or a combination thereof. In certain embodiments, the one or more siloxane-containing monomers comprise one or more linear siloxane monomers. In certain embodiments, the one or more linear siloxane monomers comprise monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, or a combination thereof. In certain embodiments, the one or more siloxane-containing monomers comprise Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane, monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, or a combination thereof. In certain embodiments, the one or more siloxane-containing monomers comprise.

[0008] a) a monomer of Formula (I) (I),

[0009] wherein

[0010] R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;

[0011] Y is -O-, -S- or -NH-;

[0012] X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,

[0013] n is an integer number selected from 0 to 100; and

[0014] m is an integer number selected from 0 to 100,

[0015] b) a monomer of Formula (II) (II),

[0016] wherein n is an integer number selected from 0 to 100,

[0017] or

[0018] c) a monomer of Formula (III), (III),

[0019] wherein:

[0020] R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;

[0021] Y is -O-, -S- or -NH-;

[0022] X is -O-, -S- , -NH-C=O-O- or -NH-C=O=NH- or -NH- ;

[0023] m is an integer number selected from 0 to 100;

[0024] n is an integer number selected from 0 to 100; and

[0025] I is an integer number selected from 0 to 100,

[0026] or a combination thereof.

[0027] In certain embodiments, the one or more siloxane-containing monomers comprise

[0028] a) a monomer of Formula (I*), (I*),

[0029] wherein:

[0030] R1is hydrogen or C1-C3alkyl;

[0031] each R2is independently C1-C4alkyl;

[0032] Y is -O-, -S- or -NH-;

[0033] X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,

[0034] n is an integer number selected from 0 to 100; and

[0035] m is an integer number selected from 0 to 100,

[0036] b) a monomer of Formula (II*) (II*),

[0037] wherein:

[0038] n is an integer number selected from 0 to 100; and

[0039] each R3is independently C1-C4alkyl,

[0040] or

[0041] c) a monomer of Formula (III*) (III*),

[0042] wherein:

[0043] R1is hydrogen or C1-C3alkyl;

[0044] Y is -O-, -S- or -NH-;

[0045] X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH- ;

[0046] each R4is independently C1-C4alkyl;

[0047] m is an integer number selected from 0 to 100;

[0048] n is an integer number selected from 0 to 100; and

[0049] I is an integer number selected from 0 to 100,

[0050] or a combination thereof.

[0051] In certain embodiments, the one or more siloxane-containing monomers comprise one or more monomers from Tables 1 and 2. In certain embodiments, the one or more siloxane-containing monomers comprise TRISMA, TRISNMA, TRISUREMA or any combination thereof. In certain embodiments, the one or more siloxane-containing monomers comprise an amide functional group, a urea functional group, an aryl group (such as phenyl or benzyl), or a combination thereof. In certain embodiments, the amide, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain). In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 5 wt% to about 98 wt% of the monomer mixture. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 30 wt% to about 95 wt% of the monomer mixture. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 50 wt% to about 90 wt% of the monomer mixture. In certain embodiments, the monomer mixture further comprises one or more siloxane-containing cross linkers. In certain embodiments, the siloxane-containing cross linkers comprise a branched (including multi-armed structures) or linear cross linker, and optionally contain a cyclic ring. In certain embodiments, the siloxane-containing cross linkers comprises one or more methacrylate- / acrylate-terminated polydimethylsiloxanes, or methacrylamide polydimethylsiloxane, or a combination thereof. In certain embodiments, the siloxane-containing cross linkers comprises methacryloxypropyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated branched polydimethylsiloxane, (3-acryloxy-2-hydroxypropoxypropyl)-terminated polydimethylsiloxane, methacrylamido propyl polydimethylsiloxane, or a combination thereof. In certain embodiments, the siloxane-containing cross linkers comprises methacylated poydimethylsiloxane. In certain embodiments, the one or more siloxane-containing cross linkers comprise one or more cross linkers selected from Table 4. In certain embodiments, the one or more siloxane-containing cross linkers comprise an amide functional group, a urea functional group, an aryl functional group (such as phenyl or benzyl), or a combination thereof. In certain embodiments, the amide functional group, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain). In certain embodiments, the one or more siloxane-containing cross linkers contributes to H-bond formulation or π–π stacking of the polymer, and optionally increase dynamic interaction. In certain embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of 0 wt% to about 50 wt% of the monomer mixture. In certain embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0 wt% to about 30 wt% of the monomer mixture. In certain embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0.01 wt% to about 50 wt% of the monomer mixture. In certain embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 1 wt% to about 10 wt% of the monomer mixture. In certain embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0.1 wt% to about 8 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers have a Tg of at least 80oC. In certain embodiments, the one or more high Tg cross linkers have a Tg of at least 100oC. In certain embodiments, the one or more high Tg cross linkers have a Tg of at least 110oC. In certain embodiments, the one or more high Tg cross linkers comprise alkyl glycol dimethacrylate such as neopentyl glycol dimethacrylate. In certain embodiments, the one or more high Tg cross linkers comprise one or more cross linkers selected from Tables 3 and 4. In certain embodiments, in the one or more high Tg cross linkers comprise a branched (including multi-armed structures) or linear cross linker, and optionally contain a cyclic ring. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least about 5 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, or at least 15 wt% of the monomer mixture.

[0052] In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 50 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most 25 wt%, at most 20 wt%, at most 18 wt%, at most 17 wt%, at most 16 wt%, at most 15 wt%, at most 14 wt%, at most 13 wt%, at most 12 wt%, at most 11 wt%, at most 10 wt% of the monomer mixture. In certain embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture. In certain embodiments, the monomer mixture further comprises one or more additional cross linkers. In certain embodiments, the one or more additional cross linkers comprise a branched (including multi-armed structures) or linear cross linker, and optionally contain a cyclic ring. In certain embodiments, the one or more additional cross linkers or high Tg cross linkers, or both comprise an amide functional group, a urea functional group, an aryl functional group (such as phenyl or benzyl), or a combination thereof. In certain embodiments, the amide functional group, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain). In certain embodiments, the one or more high Tg monomers have a Tg of at least 80oC. In certain embodiments, the one or more high Tg monomers have a Tg of at least 100oC.

[0053] In certain embodiments, the one or more high Tg monomers have a Tg of at least 110oC. In certain embodiments, the one or more high Tg monomers comprise alkyl substituted styrene monomer, adamantyl derivative, Isobronyl derivative, methacrylate, methacrylamide, or a mixture thereof. In certain embodiments, the one or more high Tg monomers comprise isobornyl acrylate, methyl methacrylate, mono, di-, tri-methyl styrene, adamantyl methacrylate, isobornyl methacrylate, or a mixture thereof In certain embodiments, the one or more high Tg monomers comprise methyl methacrylate, mono-, di-, tri-methyl styrene, adamantyl methacrylate, isobornyl methacrylate, or a mixture thereof. In certain embodiments, the one or more high Tg monomers comprise an amide functional group, a urea functional group, an aryl functional group (such as phenyl or benzyl), or a combination thereof. In certain embodiments, the amide, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain). In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture. In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of at least about 10 wt% of the monomer mixture. In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of at least 5 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, or at least 50 wt% of the monomer mixture. In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture. In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture. In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 12 wt%, at most 10 wt%, or at most 5 wt% of the monomer mixture.

[0054] In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture. In certain embodiments, the one or more high Tg monomers are present in the monomer mixture in an amount of about 5 wt% to about 70 wt% of the monomer mixture. In certain embodiments, the monomer mixture further comprises one or more UV blocking agents, one or more blue blocker agents, or a combination thereof. In certain embodiments, one or more UV blocking agents and one or more blue blocker agents are present in the monomer mixture in an amount of 0 to 1 wt% of the monomer mixture. In certain embodiments, one or more UV blocking agents and one or more blue blocker agents are present in the monomer mixture in an amount of 0 to 0.1 wt% of the monomer mixture. In certain embodiments, the siloxane-containing polymer has a Dk number of at least 80.

[0055] In certain embodiments, the siloxane-containing polymer has a Dk number of at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, or at least 200. In certain embodiments, the siloxane-containing polymer has a Dk number of at most 350. In certain embodiments, the siloxane-containing polymer has a Shore D hardness of at least 50. In certain embodiments, the siloxane-containing polymer has a Shore D hardness of at least 68. In certain embodiments, the siloxane-containing polymer has a Shore D hardness of at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75. In certain embodiments, the siloxane-containing polymer has a Shore D hardness of about 70-80. In certain embodiments, the siloxane-containing polymer does not contain fluorine. In certain embodiments, the one or more siloxane-containing monomers are non-cyclic monomers that do not contain a Si-containing cyclic ring. In certain embodiments, the ophthalmic device is a contact lens, an intraocular lens, or a corneal implant. In certain embodiments, the ophthalmic device is a contact lens. In certain embodiments, the ophthalmic device is an extended wear lens. In certain embodiments, the polymer is manufactured by in situ. In certain embodiments, the polymer is manufactured by a solvent-free process.

[0056] A material comprising the siloxane-containing polymer of the present disclosure. In certain embodiments, the materials of the present disclosure further comprising one or more additives (e.g.., dyes, UV blockers, blue blocker reagent). In certain embodiments, the present disclosure relates to a method of making a siloxane-containing polymer or a material of the present disclosure, wherein the method comprises polymerizing the monomer mixture. In certain embodiments, the method comprises curing such as thermal curing or photo curing. In certain embodiments, the method comprises solvent-free polymerization. In certain embodiments, the method comprises molding (e.g,. molding using casting and injection). In certain embodiments, the method comprises molding in a mold. In certain embodiments, the mold is a thermoplastic, thermosets, or silicon rubber. In certain embodiments, the mold has a rod shape. In certain embodiments, the mold has a button shape. In certain embodiments, the mold has a base curvature (e.g., flat and curved).

[0057] In certain aspects, the present disclosure relates to a method of producing high Tg, rigid, tough, fluorine-free and PFAS-free materials with medium to ultrahigh Dk numbers which comprises some or all:

[0058] a) One or more bulky siloxane materials with reactive moieties such as methacrylate, methacrylamide, with or without urethan or urea linkage;

[0059] b) One or more linear siloxane reactive materials with mono or multi reactive moieties;

[0060] c) One or more an alkyl glycol dimethacrylate;

[0061] c) One or more high Tg hydrophilic monomers ;

[0062] d) One or more high Tg hydrophobic monomers such as cyclic monomers (adamantyl methacrylate or Isobornyl methacrylate but not limited to) and styryl monomers such as alkyl styrene (2,4,6) tri methyl styrene;

[0063] e) UV blocking agents and blue blocker agents;

[0064] the reaction being conducted within positive pressure of inert gas from few pascal to several mega pascal using thermal or photopolymerization under temperature from 25 C to 150 c or uv to low energy lights.

[0065] INCORPORATION BY REFERENCE

[0066] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference for the specific purposes identified herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0067] The novel features of the disclosure are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the disclosure are utilized, and the accompanying drawing (also “figure” and “FIG.” herein), of which:

[0068] depicts the presence of percolated channels in the polymer materials as described herein, and a contact lens made with the percolated polymers.illustrates the permeated structure of the lens material, which allows for the selective diffusion of oxygen to the eye without the need for PFAS.

[0069] illustrates channels percolate through the bulk of a contact lens made with polymers described herein to facilitate the diffusion (transmission) of oxygen molecules (red dots) from the atmosphere to the cornea of the eye.

[0070] illustrates the structure of the polymer materials that contains percolated channels for oxygen.

[0071] illustrates the buttons made with the polymer materials of this disclosure.

[0072] illustrates the buttons and rods made with the polymer materials of Examples 1, 2, and 3.DETAILED DESCRIPTION

[0073] The following description and examples illustrate embodiments of the present disclosure in detail. It is to be understood that this present disclosure is not limited to the particular embodiments described herein and as such can vary. Those of skill in the art will recognize that there are numerous variations and modifications of this present disclosure, which are encompassed within its scope.

[0074] Although various features of the present disclosure may be described in the context of a single embodiment, the features may also be provided separately or in any suitable combination. Conversely, although the present disclosure may be described herein in the context of separate embodiments for clarity, the present disclosure may also be implemented in a single embodiment.

[0075] The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.

[0076] All terms are intended to be understood as they would be understood by a person skilled in the art. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosure pertains.

[0077] The following definitions supplement those in the art and are directed to the current application and are not to be imputed to any related or unrelated case, e.g., to any commonly owned patent or application. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing of the present disclosure, the preferred materials and methods are described herein. Accordingly, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0078] DEFINITIONS

[0079] As used in the specification and appended claims, unless specified to the contrary, the following terms have the meaning indicated below.

[0080] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an agent” includes a plurality of such agents, reference to “a stabilizer” includes a plurality of such stabilizers, and reference to “the cell” includes reference to one or more cells (or to a plurality of cells) and equivalents thereof known to those skilled in the art, and so forth. When ranges are used herein for physical properties, such as molecular weight, or chemical properties, such as chemical formulae, all combinations and subcombinations of ranges and specific embodiments therein are intended to be included.

[0081] The term “about” or “approximately” can mean within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean within 1 or more than 1 standard deviation, per the practice in the art. Alternatively, “about” can mean a range of up to 20%, up to 15%, up to 10%, up to 5%, or up to 1% of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude, within 5-fold, or within 2-fold, of a value.

[0082] The term “comprising” (and related terms such as “comprise” or “comprises” or “having” or “including”) is not intended to exclude that in other certain embodiments, for example, an embodiment of any composition of matter, composition, method, or process, or the like, described herein, “consist of” or “consist essentially of” the described features.

[0083] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances in which it does not.

[0084] Ranges provided herein are understood to be shorthand for all of the values within the range. For example, a range of 1 to 50 is understood to include any number, combination of numbers, or sub-range from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all intervening decimal values between the aforementioned integers such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, “nested sub-ranges” that extend from either end point of the range are specifically contemplated. For example, a nested sub-range of an exemplary range of 1 to 50 may comprise 1 to 10, 1 to 20, 1 to 30, and 1 to 40 in one direction, or 50 to 40, 50 to 30, 50 to 20, and 50 to 10 in the other direction.

[0085] The term “percolation threshold” means the point where the cavities in a disperse phase have a sufficient number of contact points to create a continuous network.

[0086] The term “PFAS” refers to per- and polyfluoroalkyl alkyl substances, which is a class of organic compounds in which one or more (usually, e.g., substantial portion of) hydrogens on one or more of its alkyl groups are replaced with fluorine.

[0087] As used here, the term “polymerization” or “polymer” encompasses all kind of polymerization and polymers, including e.g., homopolymer and copolymers. Accordingly, polymerization also encompasses homo-polymerization and copolymerization.

[0088] As used herein, a “high Tg” monomer or a “high Tg” cross linker refers to the monomer, or cross linker, when homo-polymerized, lead to a polymer that has a high Tg as described herein. For example, the phrase “one or more high Tgmonomers have a Tgof at least 80oC” refers to one or more monomers, when they are homo-polymerized, lead to a polymer(s) that has / have a Tgof at least 80oC. Similarly, Table 3 provides the Tg of the respective homopolymer of the cross linkers.

[0089] GAS-PERMEABLE MATERIALS

[0090] In one aspect, the disclosure relates to hyper gas-permeable materials, products comprising the materials, and methods of making and using the same. In one aspect, the present disclosure relates to ophthalmic devices (e.g., contact lenses) comprising a hyper gas-permeable material. These materials have Dk numbers on par with PFAS-containing materials and may attain Dk up to 200 and potentially above 200. These materials can be prepared in the form of rods and buttons with flat or curved bases.

[0091] Gas permeability is a product of gas solubility and diffusivity, where gas solubility strongly depends on the chemical composition of a membrane material. In current industry, replacing PFAS with other chemical structures leads to a considerable drop in Dk numbers. Therefore, there is a significant demand in PFAS-free materials that have required Dk numbers. To that end, the instant disclosure provides polymer materials that have required Dk number while not requiring PFAS component. In one aspect, the polymer materials described herein compensate less oxygen (gas) solubility by increasing gas diffusivity. In some embodiments, the polymer materials comprise percolated channels.

[0092] In the present disclosure, the enhancement of oxygen permeability is ascribed (occurs due) to the formation of percolated channels of the silicone-rich component (and) that facilitate the transmission of oxygen molecules through the bulk of a contact lens material (). The channels are formed upon microphase separation of the chemically dissimilar (distinct) polymer backbone and any non-siloxane parts from siloxane pendant groups. In addition to the chemical difference, the phase separation is mediated by two factors: (i) packing constraints of geometrically (shape-) incommensurable linear backbone and globular pendants and (ii) backbone stiffening due to steric repulsion of the bulky pendant groups and interaction of some moieties such benzyl groups, amide and urea groups. An increase in Tris volume fraction in the copolymer results in concurrent shifts in interfacial energy, packing constraints, and backbone persistent length. Jointly, these factors promote the formation of extended domains of densely packed Tris groups that propagate through the contact lens thickness, providing a passage for oxygen molecules towards the eye.

[0093] In some embodiments, disclosed herein are polymer materials comprising rigid polymer backbone. In some embodiments, disclosed herein are polymer materials comprising bulky pendant groups and interaction of some moieties such benzyl groups, amide and urea groups. In some embodiments, disclosed herein are polymer materials comprising benzyl groups, amide and urea groups. The rigidity of polymer backbone chains as well as percolation of polymer fraction with high oxygen solubility can be increased by using monomers with high glass temperature and appropriate formulations. In one aspect, disclosed herein are materials with Hyper Dk composed of high glass transition temperature (Tg) monomeric units, stiff polymer backbones, siloxane derivatives, hydrophilic reactive moieties, and assorted additives such as UV and blue light blockers. Polymerization can be conducted using thermal or photo polymerization.

[0094] The polymer materials described herein can be suitable for making contact lenses. The polymer materials described herein can also be used for other applications including applications in the ophthalmic field. The performance of a contact lens and their impact on the cornea depends on lens capability to transmit oxygen and lens wearing comfort. The gas permeability of these materials can be measured using Fick’s law and presented as oxygen transmissibility (Dk / t) for ophthalmic field. Using the Dk / t coefficient is conventional way to compare performance of contact lens in terms of oxygen permeability to have healthy eye.

[0095] In this disclosure, in one aspect, to increase the Dk of polymeric materials without using PFAS materials, the diffusivity of oxygen through the materials was enhanced by increasing free volume of polymeric network, increasing the rigidity of polymer backbone using high glass temperature monomers, and using monomer compositions that generate percolation of polymer fraction with high oxygen solubility (oxygen pathways). The disclosed materials are polymeric network with high quantity of siloxane combination with high Tg monomers that polymerized using thermal or photo initiators, activated by heat or light, respectively. The utilized monomers comprise various derivatives of siloxane, containing one or more reactive moieties such as allyl, vinyl, acrylate, methacrylate, acrylamide, meth acrylamide, norbornene but not limited to these, alkyl or aromatic hydrophobic monomers and crosslinkers, hydrophilic monomers with hydroxyl, amine or carboxylic acid reactive moieties.

[0096] The percentage of monomers with siloxane fractions can be correlated to the oxygen permeability (Dk) of the final cured materials. Adding UV and blue blocker monomers to the composition can block (considerably decrease) the percentage of UVA, UVB and high energy light, while the visible light transmission remains higher than 95%. The siloxane monomers are any siloxane derivatives monomers with above-mentioned active moieties and all siloxane derivatives that converted to the monomers and crosslinkers by reaction with meth acryloyl or acryloyl chloride and any methacrylate, methacrylamide or acrylate or acrylamide with isocyanate moieties such as methacryloethyl isocyanates but not limited to this one those can make monomers with urethane or Urea linkage. Siloxane monomers can include reactive siloxanes such as n-alkyl polydimethylsiloxane propyl methacrylate acrylate, acrylamide, methacrylamide or any other polymerizable reactive moeities), 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate; 3-[Tris(trimethylsiloxy)silyl]propyl. (3-METHACRYLOXY-2-HYDROXYPROPOXYPROPYL)METHYL BIS(TRIMETHYLSILOXY)SILANE, 3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide, polydimethylsiloxane; and monomers those driver by reaction of [Tris(trimethylsiloxy)silyl]propyl amine and acryloyl or meth acryloyl or 2-isocyano ethyl methacrylate or e-isocyano ethyl acrylamide, styrylethyltris(trimethylsiloxy)silane and any mono or bi terminated polysiloxane with methacrylate, acrylate, acryl amide, methacryl amide, and methacrylo alkyl isocyanate. These siloxane monomers are mixed with high Tg aliphatic or aromatic hydrophobic monomers such as mono, di and tri methyl styrene, admantyl methacrylate, styrene, phenolic monomers, Isobronyl methacrylate but not limited to these monomers. The cross linkers are added to the monomer mixture such as EGDMA, Bisphenol A di methacrylate, Methacrylate or acrylate or methacryl amide or acryl amide polydimethsiloxanes with molecular weight from 300 up to 10000 g / mole. Hydrophilic such as methacrylic acid or any other hydrophilic monomer with high Tg are also added to the formulation to improve the hardness and consequently the lath ability of paterials and also to have more comfortable surface using their moieties to have highly water absorbable polymer coating on the final contact lens. Uv blocker such as 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate, 2-Hydroxy-4-methacryloxybenzophenone and blue light blocker such as methacrylated acridine and tints with different colors are added to the formulation on demand. Thermal initiators such as peroxides and azo types (Luprox 26 and 256 and AIBN) are most common thermal initiators and BAPO, Irgacure 819, etc. are used as photo initiators for preparation of contact lens materials.

[0097] In one aspect, disclosed herein is a siloxane-containing polymer, which is a polymerization product of a monomer mixture. In some embodiments, the monomer mixture comprises one or more high Tgcross linkers. In some embodiments, the monomer mixture comprises one or more high Tgmonomers. In some embodiments, the monomer mixture comprises one or more siloxane-containing monomers. In some embodiments, the monomer mixture comprises an aryl group such as benzyl or phenyl. In some embodiments, the monomer mixture comprises amide groups. In some embodiments, the monomer mixture comprises urea groups. In some embodiments, the monomer mixture comprises a rigid polymer backbone. In some embodiments, the monomer mixture is substantially free of PFAS material. In some embodiments, the monomer mixture is free of PFAS material.

[0098] In one aspect, the present disclosure relates to a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising:one or more high Tgcross linkers;one or more high Tgmonomers; andone or more siloxane-containing monomers;wherein the siloxane-containing polymer has a Dk number of at least 45.

[0099] In some embodiments, the siloxane-containing polymer comprises a percolation structure. In some embodiments, the siloxane-containing polymer comprises a percolation structure that exceeds a percolation threshold.

[0100] In some embodiments, the monomer mixture is substantially free of PFAS material. In some embodiments, the monomer mixture is free of PFAS material.

[0101] In one aspect, the present disclosure relates to a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising:one or more high Tgcross linkers;one or more high Tgmonomers; andone or more siloxane-containing monomers;wherein the siloxane-containing polymer comprises a percolation structure.

[0102] In some embodiments, the percolation structure exceeds a percolation threshold. In some embodiments, the percolation structure are channels. In some embodiments, the percolation structure are percolated channels. In some embodiments, the percolation threshold is sufficient to allow the permeation of oxygen. In some embodiments, the percolated channels are formed upon microphase separation of the siloxane-containing polymer. In some embodiments, a siloxane-containing polymer described herein comprise phase separation. In some embodiments, a siloxane-containing polymer described herein comprise microphase separation.

[0103] Exemplary siloxane-containing polymers as describe herein are provided in Ex 1 to Ex 63.

[0104] In some embodiments, the siloxane-containing polymer has a Dk number of at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, or at least 200. In some embodiments, the siloxane-containing polymer has a Dk number of at least 30. In some embodiments, the siloxane-containing polymer has a Dk number of at least 40. In some embodiments, the siloxane-containing polymer has a Dk number of at least 50. In some embodiments, the siloxane-containing polymer has a Dk number of at least 60. In some embodiments, the siloxane-containing polymer has a Dk number of at least 70. In some embodiments, the siloxane-containing polymer has a Dk number of at least 80. In some embodiments, the siloxane-containing polymer has a Dk number of at least 90. In some embodiments, the siloxane-containing polymer has a Dk number of at least 100. In some embodiments, the siloxane-containing polymer has a Dk number of at least 110. In some embodiments, the siloxane-containing polymer has a Dk number of at least 120. In some embodiments, the siloxane-containing polymer has a Dk number of at least 130. In some embodiments, the siloxane-containing polymer has a Dk number of at least 140. In some embodiments, the siloxane-containing polymer has a Dk number of at least 150. In some embodiments, the siloxane-containing polymer has a Dk number of at least 160. In some embodiments, the siloxane-containing polymer has a Dk number of at least 170. In some embodiments, the siloxane-containing polymer has a Dk number of at least 180. In some embodiments, the siloxane-containing polymer has a Dk number of at least 190. In some embodiments, the siloxane-containing polymer has a Dk number of at least 200. In some embodiments, the siloxane-containing polymer has a Dk number of at least 210. In some embodiments, the siloxane-containing polymer has a Dk number of at least 220. In some embodiments, the siloxane-containing polymer has a Dk number of at least 230. In some embodiments, the siloxane-containing polymer has a Dk number of at least 240. In some embodiments, the siloxane-containing polymer has a Dk number of at least 250. In some embodiments, the siloxane-containing polymer has a Dk number of at least 260. In some embodiments, the siloxane-containing polymer has a Dk number of at least 270. In some embodiments, the siloxane-containing polymer has a Dk number of at least 280. In some embodiments, the siloxane-containing polymer has a Dk number of at least 290. In some embodiments, the siloxane-containing polymer has a Dk number of at least 300. In some embodiments, the siloxane-containing polymer has a Dk number of at least 310. In some embodiments, the siloxane-containing polymer has a Dk number of at least 320. In some embodiments, the siloxane-containing polymer has a Dk number of at least 330. In some embodiments, the siloxane-containing polymer has a Dk number of at least 340. In some embodiments, the siloxane-containing polymer has a Dk number of at least 350. In some embodiments, the siloxane-containing polymer has a Dk number of at most 350. In some embodiments, the siloxane-containing polymer has a Dk number of at most 340. In some embodiments, the siloxane-containing polymer has a Dk number of at most 330. In some embodiments, the siloxane-containing polymer has a Dk number of at most 320. In some embodiments, the siloxane-containing polymer has a Dk number of at most 310. In some embodiments, the siloxane-containing polymer has a Dk number of at most 300. In some embodiments, the siloxane-containing polymer has a Dk number of at most 290. In some embodiments, the siloxane-containing polymer has a Dk number of at most 280. In some embodiments, the siloxane-containing polymer has a Dk number of at most 270. In some embodiments, the siloxane-containing polymer has a Dk number of at most 260. In some embodiments, the siloxane-containing polymer has a Dk number of at most 250. In some embodiments, the siloxane-containing polymer has a Dk number of at most 240. In some embodiments, the siloxane-containing polymer has a Dk number of at most 220. In some embodiments, the siloxane-containing polymer has a Dk number of at most 210. In some embodiments, the siloxane-containing polymer has a Dk number of at most 200. In some embodiments, the siloxane-containing polymer has a Dk number of at most 190. In some embodiments, the siloxane-containing polymer has a Dk number of at most 180. In some embodiments, the siloxane-containing polymer has a Dk number of at most 170. In some embodiments, the siloxane-containing polymer has a Dk number of at most 160. In some embodiments, the siloxane-containing polymer has a Dk number of at most 150.

[0105] In some embodiments, the siloxane-containing polymer has a Dk number of about 100 to 200. In some embodiments, the siloxane-containing polymer has a Dk number of about 100 to 150. In some embodiments, the siloxane-containing polymer has a Dk number of about 150 to 200. In some embodiments, the siloxane-containing polymer has a Dk number of about 180 to 220.

[0106] In some embodiments, the siloxane-containing polymer has a Shore D hardness of at least 70. In some embodiments, the siloxane-containing polymer has a Shore D hardness of at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75. In some embodiments, the siloxane-containing polymer has a Shore D hardness of about 70-80. In some embodiments, the siloxane-containing polymer has a Shore D hardness of about 65-85.

[0107] In some embodiments, the siloxane-containing polymer is not cloudy after curing. In some embodiments, the siloxane-containing polymer remains transparent after curing. In some embodiments, the siloxane-containing polymer remains transparent after storing at room temperature for about 1 week, 1 month, 3 months, 6 months, 9 months, 1 year, 2 years, 3 years, 4 year, 5 years, 6 years, or 7 years.

[0108] In some embodiments, the siloxane-containing polymer is substantially free of PFAS material. In some embodiments, the siloxane-containing polymer comprises at most 0.001 wt%, at most 0.01 wt%, at most 0.1 wt%, at most 0.5 wt%, or at most 1 wt% of PFAS material. In some embodiments, the siloxane-containing polymer comprises at most 5 wt% of PFAS material. In some embodiments, the siloxane-containing polymer is free of PFAS material. In some embodiments, PFAS material may be added in the polymer.

[0109] In some embodiments, the oxygen permeation of the siloxane-containing polymer is provided by percolation, and thus PFAS material is not required in the polymer for permeation.

[0110] In some embodiments, halogen or fluorine containing monomer or material may be added in the polymer.For example, in some embodiments, the siloxane-containing polymer does not contain fluorine. In some embodiments, fluorine may be added in the polymer. In some embodiments, the siloxane-containing polymer comprises at most 0.001 wt%, at most 0.01 wt%, at most 0.1 wt%, at most 0.5 wt%, or at most 1 wt% of halogen or fluorine containing monomer or material. In some embodiments, the siloxane-containing polymer comprises at most 5 wt of halogen or fluorine containing monomer or material.

[0111] In certain embodiments, a herein described siloxane-containing polymer is selected from Tables E1 and E2.

[0112] In certain embodiments, a herein described siloxane-containing polymer is a polymerization product of a monomer mixture comprising: one or more high Tgcross linkers (e.g., comprising Neopentyl glycol dimethacrylate (NGDMA)); one or more high Tgmonomers comprising styrylethyltris(trimethylsiloxy)silane (Tris styrene) and methacrylic acid; and one or more siloxane-containing monomers comprising TRISMA and optionally methacylated polydimethylsiloxane. In certain embodiments, the one or more high Tgcross linkers comprise Neopentyl glycol dimethacrylate. In certain embodiments, the one or more high Tgcross linkers (e.g., Neopentyl glycol dimethacrylate) are present in the monomer mixture in an amount of about 5 wt% to about 15 wt%. In certain embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of about 2 wt % to about 20 wt%. In certain embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 10 wt% to about 20 wt%. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 60 wt% to about 80 wt%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 50 wt% to about 90%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 60 wt% to about 80%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 65 wt% to about 70 wt%. In certain embodiments, Tris styrene is present in the monomer mixture in an amount of about 5% to about 15%. In certain embodiments, Tris styrene is present in the monomer mixture in an amount of about 2% to about 20%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 1% to about 15%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 3% to about 8%. In certain embodiments, the monomer mixture further comprises methacylated polydimethylsiloxane. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 3% to about 8%.

[0113] In certain embodiments, a herein described siloxane-containing polymer is a polymerization product of a monomer mixture comprising: one or more high Tgcross linkers (e.g., comprising Neopentyl glycol dimethacrylate (NGDMA)); one or more high Tgmonomers comprising styrylethyltris(trimethylsiloxy)silane (Tris styrene) and methacrylic acid; and one or more siloxane-containing monomers comprising TRISMA, Tris methacylamide, and optionally methacylated polydimethylsiloxane. In certain embodiments, the one or more high Tgcross linkers comprise Neopentyl glycol dimethacrylate. In certain embodiments, the one or more high Tgcross linkers (e.g., Neopentyl glycol dimethacrylate) are present in the monomer mixture in an amount of about 5 wt% to about 15 wt%. In certain embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of about 2 wt % to about 20 wt%. In certain embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 10 wt% to about 20 wt%. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 60 wt% to about 80 wt%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 50 wt% to about 90%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 60 wt% to about 80%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 62 wt% to about 68 wt%. In certain embodiments, Tris methacylamide is present in the monomer mixture in an amount of about 0.5 wt% to about 10 wt%. In certain embodiments, Tris methacylamide is present in the monomer mixture in an amount of about 1 wt% to about 8 wt%. In certain embodiments, Tris methacylamide is present in the monomer mixture in an amount of about 3 wt% to about 8 wt%. In certain embodiments, Tris styrene is present in the monomer mixture in an amount of about 5% to about 15%. In certain embodiments, Tris styrene is present in the monomer mixture in an amount of about 2% to about 20%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 1% to about 15%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 3% to about 8%. In certain embodiments, the monomer mixture further comprises methacylated polydimethylsiloxane. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 3% to about 8%.

[0114] In certain embodiments, a herein described siloxane-containing polymer is a polymerization product of a monomer mixture comprising: one or more high Tgcross linkers (e.g., comprising Neopentyl glycol dimethacrylate (NGDMA)); one or more high Tgmonomers comprising Me3 styrene and methacrylic acid; and one or more siloxane-containing monomers comprising TRISMA and optionally methacylated polydimethylsiloxane. In certain embodiments, the one or more high Tgcross linkers comprise Neopentyl glycol dimethacrylate. In certain embodiments, the one or more high Tgcross linkers (e.g., Neopentyl glycol dimethacrylate) are present in the monomer mixture in an amount of about 5 wt% to about 15 wt%. In certain embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of about 2 wt % to about 20 wt%. In certain embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 10 wt% to about 20 wt%. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 60 wt% to about 80 wt%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 50 wt% to about 90%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 60 wt% to about 80%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 65 wt% to about 70 wt%. In certain embodiments, Me3 styrene is present in the monomer mixture in an amount of about 5% to about 15%. In certain embodiments, Me3 styrene is present in the monomer mixture in an amount of about 8% to about 12%. In certain embodiments, Me3 styrene is present in the monomer mixture in an amount of about 2% to about 20%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 1% to about 15%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacrylic acid is present in the monomer mixture in an amount of about 3% to about 8%. In certain embodiments, the monomer mixture further comprises methacylated polydimethylsiloxane. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 3% to about 8%.

[0115] In certain embodiments, a herein described siloxane-containing polymer is a polymerization product of a monomer mixture comprising: one or more high Tgcross linkers (e.g., comprising Ethyleneglycol methacrylate (mono-penta)); one or more high Tgmonomers comprising Me3 styrene and Tris styrene; and one or more siloxane-containing monomers comprising TRISMA and optionally methacylated polydimethylsiloxane. In certain embodiments, the one or more high Tgcross linkers comprise Ethyleneglycol methacrylate (mono-penta). In certain embodiments, the one or more high Tgcross linkers (e.g., Ethyleneglycol methacrylate (mono-penta)) are present in the monomer mixture in an amount of about 5 wt% to about 15 wt%. In certain embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of about 2 wt % to about 20 wt%. In certain embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 10 wt% to about 20 wt%. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 60 wt% to about 80 wt%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 50 wt% to about 90%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 60 wt% to about 80%. In certain embodiments, TRISMA is present in the monomer mixture in an amount of about 65 wt% to about 70 wt%. In certain embodiments, Me3 styrene is present in the monomer mixture in an amount of about 5% to about 15%. In certain embodiments, Me3 styrene is present in the monomer mixture in an amount of about 2% to about 8%. In certain embodiments, Me3 styrene is present in the monomer mixture in an amount of about 2% to about 20%. In certain embodiments, Tris styrene acid is present in the monomer mixture in an amount of about 1% to about 15%. In certain embodiments, Tris styrene is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, Tris styrene is present in the monomer mixture in an amount of about 5% to about 15%. In certain embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 10% to about 20%. present in the monomer mixture in an amount of about 5% to about 25%. In certain embodiments, the monomer mixture further comprises methacylated polydimethylsiloxane. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 1% to about 10%. In certain embodiments, methacylated polydimethylsiloxane is present in the monomer mixture in an amount of about 3% to about 8%.

[0116] Siloxane-containing monomers

[0117] In some embodiments, a siloxane-containing polymer described herein is a polymerization product of a monomer mixture, wherein the monomer mixture comprises one or more siloxane-containing monomers.

[0118] In some embodiments, the one or more siloxane-containing monomers comprise one or more bulky siloxane monomers. In some embodiments, the one or more siloxane-containing monomers comprise one or more linear siloxane monomers.

[0119] In some embodiments, the one or more siloxane-containing monomers comprise a monomer of Formula (I), a monomer of Formula (II), or a monomer of Formula (III), or a mixture thereof. In some embodiments, the one or more siloxane-containing monomers comprise a monomer of Formula (I*), a monomer of Formula (II*), or a monomer of Formula (III*), or a mixture thereof.

[0120] In some embodiments, the one or more siloxane-containing monomers comprise a bulky siloxane monomer of prepolymer having an ethylenically unsaturated reactive group.

[0121] In some embodiments, the one or more siloxane-containing monomers comprise a monofunctional silicone monomer having an ethylenically unsaturated reactive group.

[0122] In some embodiments, the siloxane-containing polymer comprises siloxane monomers with reactive moieties such as allyl, vinyl, acrylate and methacrylate, for example, a monomer of Formula (I*), (I), (II*), (II), (III*), or (III) as described below.

[0123] In some embodiments, described herein is a siloxane-containing monomer of Formula (I*),

[0124] Formula (I*)

[0125] wherein:

[0126] R1is hydrogen or C1-C3alkyl;

[0127] each R2is independently C1-C4alkyl;

[0128] Y is -O-, -S- or -NH-;

[0129] X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,

[0130] n is an integer number selected from 0 to 100; and

[0131] m is an integer number selected from 0 to 100.

[0132] In some embodiments, described herein is a siloxane-containing monomer of Formula (I),

[0133] Formula (I)

[0134] wherein

[0135] R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;

[0136] Y is -O-, -S- or -NH-;

[0137] X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,

[0138] n is an integer number selected from 0 to 100; and

[0139] m is an integer number selected from 0 to 100.

[0140] In some embodiments, described herein is a siloxane-containing monomer of Formula (II*),

[0141] Formula (II*)

[0142] wherein:

[0143] n is an integer number selected from 0 to 100; and

[0144] each R3is independently C1-C4alkyl.

[0145] In some embodiments, described herein is a siloxane-containing monomer of Formula (II),

[0146] Formula (II)

[0147] wherein n is an integer number selected from 0 to 100.

[0148] In some embodiments, described herein is a siloxane-containing monomer of Formula (III*),

[0149] Formula (III*)

[0150] wherein

[0151] R1is hydrogen or C1-C3alkyl;

[0152] Y is -O-, -S- or -NH-;

[0153] X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH- ;

[0154] each R4is independently C1-C4alkyl;

[0155] n is an integer number selected from 0 to 100;

[0156] I is an integer number selected from 0 to 100; and

[0157] m is an integer number selected from 0 to 100.

[0158] In some embodiments, described herein is a siloxane-containing monomer of Formula (III),

[0159] Formula (III)

[0160] wherein

[0161] R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;

[0162] Y is -O-, -S- or -NH-;

[0163] X is -O-, -S- , -NH-C=O-O- or -NH-C=O=NH- or -NH- ;

[0164] n is an integer number selected from 0 to 100;

[0165] I is an integer number selected from 0 to 100; and

[0166] m is an integer number selected from 0 to 100.

[0167] In some embodiments, the siloxane-containing monomer comprises a bulky siloxane (e.g., monomers of Formula (I*), (I), (II*), or (II)).

[0168] In some embodiments, the siloxane-containing monomer is selected from the monomers of Formula (I). In some embodiments, the siloxane-containing monomer is selected from the monomers of Formula (I*). In some embodiments, the siloxane-containing monomer is selected from the monomers of Formula (II). In some embodiments, the siloxane-containing monomer is selected from the monomers of Formula (II*).

[0169] In some embodiments, the siloxane-containing monomer comprises a linear siloxane chain (e.g., monomers of Formula (III*) or (III)).

[0170] In some embodiments, the siloxane-containing monomer is selected from the monomers of Formula (III). In some embodiments, the siloxane-containing monomer is selected from the monomers of Formula (III*).

[0171] In some embodiments, a bulky siloxane monomer is selected from the monomers in Table 1.

[0172] Table 1. Exemplary bulky siloxane monomerNameStructure3-[Tris(trimethylsiloxy)silyl]propyl methacrylate(“TrisMA” or “TRISMA”) 3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide("Tris methacylamide” or “TRISNMA”) 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate with Urea linker("TrisUrea”) (3-methacrylamidopropyl)bis(trimethylsiloxy)methylsilane (3-methacryloxy-2-hydroxypropoxypropyl)methyl bis(trimethylsiloxy)silane methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane, tec (methacryloxypropyl)methylsiloxane] - dimethylsiloxane copolymerMn= 500-10000 g / mole methacryloxypropyl t-structure siloxane or polysiloxanes, di-Me, [[[3-[(2-methyl-1-oxo-2-propenyl)oxy]propyl]silylidyne]tris(oxy)]tris Styrylethyltris(trimethylsiloxy)silane, mixed isomers PSS-(1-Propylmethacrylate)-Heptaisobutyl substituted Methacryloxypropylbis(trimethylsiloxy)silanol Acrylamidopropyltris(trimethylsiloxy)silane (3-Methacrylamidopropyl)bis(trimethylsiloxy)methylsilane Monomethacryloxypropyl Functional PolydimethylsiloxaneMn=500-10000 g / mole trimethoxy(4-vinylphenyl)silane

[0173] Representative examples of siloxane-containing monomers include monomethacryoxypropyl terminated polydimethylsiloxane, asymmetric 3-methacryloyloxypropyltris(trimethylsiloxy)silane or tris(trimethylsiloxy)silylpropyl methacrylate (TRIS), tris(trimethylsiloxy)silylpropyl vinyl carbamate, (TRIS-VC), pentamethyldisiloxanyl methylmethacrylate, phenyltetramethyl-disiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane, (3-methacryloxy-2-hydroxypropoxypropyl)methyl bis(trimethylsiloxy)silane (3-methacryloxy-2-hydroxy propoxy)propyl bis(trimethyl siloxy)methyl silane (Sigma) and mixtures thereof.

[0174] In some embodiments, the one or more bulky siloxane monomers comprise methacryloxypropyltris(trimethylsiloxy)silane, (3-methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, acrylamidopropyltris(trimethylsiloxy)silane, or a combination thereof.

[0175] In some embodiments, the one or more siloxane-containing monomers comprise one or more linear siloxane monomers.

[0176] In some embodiments, the one or more linear siloxane monomers comprise mono-methacryloxypropyl-terminated PDMS, mono-methacryloxypropyl branched PDMS, or a combination thereof.

[0177] In some embodiments, the one or more linear siloxane monomers comprise a monomer of Table 2.

[0178] Table 2. Exemplary Linear siloxane monomersNameStructuremonoMETHACRYLOXYPROPYL TERMINATED POLYDIMETHYLSILOXANE, asymmetricMn =150-10000 g / mole R1is C1-3alkylR2is C1-6alkyln = 0-100monoMethacrylamidopropylterminated polydimethylsiloxane, asymmetric R1is C1-3alkylR2is C1-6alkyln = 0-100NA R1is C1-3alkylR2is C1-4alkyln = 0-100NA R1is C1-3alkylR2is C1-6alkyln = 0-100NA R1is C1-3alkylR2is C1-6alkyln = 0-100NA R1is C1-3alkylR2is C1-6alkyln = 0-100

[0179] In some embodiments, the one or more siloxane-containing monomers comprise methacryloxypropyltris(trimethylsiloxy)silane, (3-methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, methacryloxypropylbis(trimethylsiloxy)silanol, acrylamidopropyltris(trimethylsiloxy)silane, mono-methacryloxypropyl-terminated PDMS, mono-methacryloxypropyl branched PDMS, or a combination thereof.

[0180] In some embodiments, siloxane monomers such as tris(trimethylsiloxy) silane is present in the monomer mixture in an amount of about 0-85 wt%. In some embodiments, styryltris(trimethylsiloxy)silane or any other styrylalkyltris(trimethylsiloxy)silane is present in the monomer mixture in an amount of about 0 to 85 wt%. In some embodiments, bifunctional poly dialkyls siloxane such as methacrylate terminated polydimethyl siloxane or any other alkyl siloxane and any alkyl di alkyl siloxane such ad ethylene di methyl siloxane present in the monomer mixture in an amount of from 0 to 20 wt %. Siloxane monomers can be mixed with high Tg hydrophilic and hydrophobic monomers and cross linkers such as methacrylic acid, alkyl substituted styrene monomers, cyclic monomers such adamantyl methacrylate, isobronyl methacrylte (which can be present in the monomer mixture in an amount of abou 0 to 50 wt%.)

[0181] In some embodiments, a siloxane-containing monomer described herein comprises an amide functional group. In some embodiments, a siloxane-containing monomer described herein comprises a urea functional group. In some embodiments, a siloxane-containing monomer described herein comprises an aryl group (such as phenyl or benzyl).

[0182] In some embodiments, the one or more siloxane-containing monomers comprise (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate) (TRISMA). In some embodiments, the one or more siloxane-containing monomers comprise (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide) (TRISNMA). In some embodiments, the one or more siloxane-containing monomers comprise (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylate (TRISUREMA). In some embodiments, the one or more siloxane-containing monomers comprise TRISMA, TRISNMA, TRISUREMA or any combination thereof.

[0183] In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 5 wt% to about 98 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 30 wt% to about 95 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 50 wt% to about 90 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 55 wt% to about 90 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 60 wt% to about 85 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 60 wt% to about 85 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are bulky siloxane-containing monomers.

[0184] In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of at least 30 wt%, 40 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, or 85 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are present in the monomer mixture in an amount of at most 99 wt%, 95 wt%, 90 wt%, 88 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, or 65 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing monomers are bulky siloxane-containing monomers.

[0185] In some embodiments, one or more linear siloxane-containing monomers are present in the monomer mixture in an amount of less than 20 wt%. In some embodiments, one or more linear siloxane-containing monomers are present in the monomer mixture in an amount of less than 15 wt%. In some embodiments, one or more linear siloxane-containing monomers are present in the monomer mixture in an amount of less than 10 wt%. In some embodiments, one or more linear siloxane-containing monomers are present in the monomer mixture in an amount of less than 5 wt%. In some embodiments, one or more linear siloxane-containing monomers are present in the monomer mixture in an amount of 0 to 15 wt%. In some embodiments, one or more linear siloxane-containing monomers are selected from Table 2.

[0186] In some embodiments, TRISMA is present in the monomer mixture in an amount of about 50 wt% to about 60 wt% of the monomer mixture. In some embodiments, TRISMA is present in the monomer mixture in an amount of about 55 wt% to about 80 wt% of the monomer mixture. In some embodiments, TRISMA is present in the monomer mixture in an amount of about 60 wt% to about 70 wt% of the monomer mixture.

[0187] High Tg monomer

[0188] In some embodiments, a siloxane-containing polymer described herein is a polymerization product of a monomer mixture, wherein the monomer mixture comprises one or more high Tgmonomers.

[0189] In some embodiments, the one or more high Tgmonomers have a Tgof at least 80oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 100oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 110oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 120oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 130oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 140oC.

[0190] In some embodiments, the one or more high Tgmonomers have a Tgof at least 150oC. In some embodiments, the one or more high Tg monomers have a Tg of at least 155oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 160oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 165oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 170oC. In some embodiments, the one or more high Tgmonomers have a Tgof at least 180oC.

[0191] In some embodiments, the one or more high Tgmonomers comprise alkyl substituted styrene monomer, adamantyl derivative, isobronyl derivative, methacrylate, methacrylamide, or a mixture thereof. In some embodiments, the one or more high Tgmonomers comprise alkyl substituted styrene monomer. In some embodiments, the one or more high Tgmonomers comprise adamantyl derivative. In some embodiments, the one or more high Tgmonomers comprise isobronyl derivative. In some embodiments, the one or more high Tgmonomers comprise methacrylate. In some embodiments, the one or more high Tgmonomers comprise methacrylamide.

[0192] In some embodiments, the one or more high Tgmonomers comprise methacrylic acid, mono-, bi-, tri-methylstyrene, adamantyl methacrylate, isobornyl methacrylate, or a mixture thereof. In some embodiments, the one or more high Tgmonomers comprise methacrylic acid. In some embodiments, the one or more high Tgmonomers comprise methacrylic acid, mono-, bi-, tri-methylstyrene, adamantyl methacrylate, isobornyl methacrylate, isobornyl acrylate, or a mixture thereof. In some embodiments, the one or more high Tgmonomers comprise methacrylic acid. In some embodiments, the one or more high Tgmonomers comprise a methacrylate, an acrylate monomer, a vinyl monomer, allyl monomer, or a mixture thereof.

[0193] In some embodiments, a high Tgmonomer described herein comprises an amide functional group. In some embodiments, a high Tgmonomer described herein comprises a urea functional group. In some embodiments, a high Tgmonomer described herein comprises an aryl group (such as phenyl or benzyl).

[0194] In some embodiments, the one or more high Tgmonomers comprise styrene. In some embodiments, the one or more high Tgmonomers comprise 2, 4, 6 trimethylstyrene (Me3 styrene). In some embodiments, the one or more high Tgmonomers comprise tris Styrene (styrylethyltris(trimethylsiloxy)silane). In some embodiments, the one or more high Tgmonomers comprise methacrylic acid. In some embodiments, the one or more high Tgmonomers comprise adamantyl methacrylate. In some embodiments, the one or more high Tgmonomers comprise isobrony / e methacrylate. In some embodiments, the one or more high Tgmonomers comprise 2, 4, 6-trimethylstyrene, tris Styrene (styrylethyltris(trimethylsiloxy)silane), methacrylic acid, adamantyl methacrylate, isobrony / e methacrylate, or a combination thereof. In some embodiments, the one or more high Tgmonomers comprise Me3 Styrene, admantyl derivatives acrylate or methacrylate, Bronyl acrylate methacrylate, methacrylic acid, methyl methacrylate, or a combination thereof.

[0195] In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of at least about 10 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of at least 5 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, or at least 50 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 12 wt%, at most 10 wt%, or at most 5 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 10 wt% to about 15 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 11 wt% to about 12 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 8 wt% to about 20 wt% of the monomer mixture. In some embodiments, the one or more high Tgmonomers are present in the monomer mixture in an amount of about 10 wt% to about 20 wt% of the monomer mixture.

[0196] Cross linkers

[0197] In some embodiments, a siloxane-containing polymer described herein is a polymerization product of a monomer mixture, wherein the monomer mixture comprises one or more cross linkers. In some embodiments, the monomer mixture comprises one or more siloxane-containing cross linkers. In some embodiments, the monomer mixture comprises one or more cross linkers that do not contain siloxane. In some embodiments, the monomer mixture comprises one or more high Tgcross linkers. In some embodiments, the cross linkers that do not contain siloxane are high Tgcross linkers. In some embodiments, the siloxane-containing cross linkers are high Tgcross linkers. In some embodiments, all the cross linkers are high Tgcross linkers. In some embodiments, the one or more cross linkers comprises one or more cross linker of Table 3. In some embodiments, the one or more cross linkers comprises one or more cross linker of Table 4.

[0198] In some embodiments, the siloxane-containing cross linkers comprises methacrylate- / acrylate-terminated polydimethylsiloxanes, or methacrylamide polydimethylsiloxane, or a combination thereof.

[0199] In some embodiments, the siloxane-containing cross linkers comprises methacryloxypropyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated branched polydimethylsiloxane, (3-acryloxy-2-hydroxypropoxypropyl)-terminated polydimethylsiloxane, or methacrylamidopropylpolydimethylsiloxane, or a combination thereof.

[0200] In some embodiments, the siloxane-containing cross linkers comprises methacylated polydimethylsiloxane.

[0201] In some embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of 0 wt% to about 50 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0.01 wt% to about 50 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 1 wt% to about 10 wt% of the monomer mixture. In some embodiments, the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 3 wt% to about 8 wt% of the monomer mixture.

[0202] In some embodiments, the one or more high Tgmonomers comprise Neopentyldimethacrylate. In some embodiments, the one or more high Tgmonomers comprise monomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M12). In some embodiments, the one or more high Tgmonomers comprise monomethacrylamido terminated polydimethylsiloxane. In some embodiments, the one or more high Tgmonomers comprise polydimethylsiloxane dimethacrylate. In some embodiments, the one or more high Tgmonomers comprise polydimethylsiloxane dimethacrylamide. In some embodiments, the one or more high Tgmonomers comprise Neopentyldimethacrylate, monomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M12), monomethacrylamido terminated polydimethylsiloxane, polydimethylsiloxane dimethacrylate, polydimethylsiloxane dimethacrylamide, or a combination thereof.

[0203] In some embodiments, a cross linker described herein comprises an amide functional group. In some embodiments, a cross linker described herein comprises a urea functional group. In some embodiments, a cross linker described herein comprises an aryl group (such as phenyl or benzyl).

[0204] In some embodiments, the one or more cross linkers comprises a branched cross linker.

[0205] In some embodiments, the one or more cross linkers comprises one or more high Tgcross linkers of Table 3. In some embodiments, the one or more cross linkers comprises one or more cross linker of Table 4.

[0206] Table 3. Exemplary high Tgcross linkersNameStructureGlass transition temperatureCross linking densityMol / m3Ethylene glycol dimethacrylate(EGDMA) 130.710719.4Diethylene glycol dimethacrylateDEGDMA 152.83660Diethylene glycol dimethacrylamide each R1is independently C1-3alkyl or HTriethylene glycol dimethacrylateTEGDMA 141.1±1.13420Tetraethylene glycol dimethacrylateT4EGDMA 131.2±2.638201,6-hexanediol dimethacrylate1,6-HDMA 150.0±4.854001,4-butanediol dimethacrylate1,4-BDMA 147.8±4.377901,3-butanediol dimethacrylate1,3-BDMA 153.7±2.618500Neopentyl glycol dimethacrylateNGDMA 168.3±2.04990PentaerythritolImethacrylatePEDMA 154.7±8.25190TrimethylolpropaneTrimethacrylateTMTMA 156±2.617400PentaerythritolTrimethacrylatePETMA 155.2±4.1114001,3-glycerolDimethacrylateGDMA 166.0±1.26830Glyceryltrimethacrylate-164.2±3.326400Bisphenol AethoxylatedimethacrylateBisEMA 111.1±1.91870DiurethaneDimethacrylateUDMA 130.6±0.82250DAEBPADiallylether Bisphenol AnD25 = 1.563 O-DABPAOrtho diallyl Bisphenol AnD25 = 1.580

[0207] Table 4. Exemplary of siloxane cross linkersNameStructure1 each R1is independently C1-3alkyln is an integer selected from 0-1002 each R1is independently C1-3alkyln is an integer selected from 0-1003 each R1is independently C1-3alkyleach R2is independently C1-4alkylamine or C1-4alkoxyn is an integer selected from 0-1004 each R1is independently C1-3alkyleach R2is independently C1-4alkylamine or C1-4alkoxyn is an integer selected from 0-1005 6 R1, R2and R3are independent C1-4alkyl, benzyl, acrylate, or methacrylate7 8 each R1is independently C1-3alkyl

[0208] In some embodiments, the one or more high Tgcross linkers have a Tgof at least 80oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 100oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 110oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 120oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 130oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 140oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 150oC. In some embodiments, the one or more high Tg cross linkers have a Tg of at least 155oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 160oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 165oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 170oC. In some embodiments, the one or more high Tgcross linkers have a Tgof at least 180oC.

[0209] In some embodiments, the one or more high Tgcross linkers comprise alkyl glycol dimethacrylate such as neopentyl glycol dimethacrylate. In some embodiments, the one or more high Tgcross linkers comprise 1, 3 glyceryl dimethacrylate, 1,4 butanodiol di methacrylate, diethyleneblycol dimethacrylate, or a combination thereof. In some embodiments, the one or more high Tgcross linkers comprise neopentyldimethacrylate. In some embodiments, the one or more high Tgcross linkers comprise 1, 3 glyceryl dimethacrylate, 1,4 butanodiol di methacrylate, diethyleneblycol dimethacrylate, neopentyldimethacrylate, or a combination thereof. In some embodiments, the one or more high Tgcross linkers comprise dimethacrylate.

[0210] In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture. In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of at least about 5 wt% of the monomer mixture.

[0211] In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, at least 15 wt%, at least 20 wt%, , at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, or at least 50 wt% of the monomer mixture.

[0212] In some embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 50 wt% of the monomer mixture. In some embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 45 wt% of the monomer mixture. In some embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 40 wt% of the monomer mixture. In some embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 35 wt% of the monomer mixture. In some embodiments, the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 30 wt% of the monomer mixture. In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture. In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture. In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 18 wt%, at most 17 wt%, at most 16 wt%, at most 15 wt%, at most 14 wt%, at most 13 wt%, at most 12 wt%, at most 11 wt%, or at most 10 wt% of the monomer mixture.

[0213] In some embodiments, the one or more high Tgcross linkers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt%, 5 wt% to about 13 wt%, 5 wt% to about 11 wt%, 5 wt% to about 9 wt%, 5 wt% to about 7 wt%, 6 wt% to about 15 wt%, 6 wt% to about 13 wt%, 6 wt% to about 11 wt%, 6 wt% to about 9 wt%, 7 wt% to about 15 wt%, 7 wt% to about 13 wt%, 7 wt% to about 11 wt%, 7 wt% to about 9 wt%, 8 wt% to about 15 wt%, 8 wt% to about 13 wt%, 8 wt% to about 11 wt%, 8 wt% to about 9 wt%, 9 wt% to about 15 wt%, 9 wt% to about 13 wt%, 9 wt% to about 11 wt%, 10 wt% to about 15 wt%, 10 wt% to about 13 wt%, or 10 wt% to about 11 wt% of the monomer mixture.

[0214] In some embodiments, a monomer mixture described herein comprises one or more additional cross linkers. In some embodiments, a monomer mixture described herein comprises one or more cross linkers that are not considered having a high Tg. In some embodiments, a monomer mixture described herein comprises a cross linker having a Tgof less than 50oC, 60oC, 70oC, 80oC, 90oC, 100oC, 110oC, 120oC, 130oC, 140oC, or 150oC.

[0215] In some embodiments, the one or more cross linkers without high Tgare present in the monomer mixture in an amount of about 0 wt% to about 90 wt%, about 0 wt% to about 80 wt%, about 0 wt% to about 70 wt%, about 0 wt% to about 60 wt%, about 0 wt% to about 50 wt%, about 0 wt% to about 40 wt%, about 0 wt% to about 30 wt%, about 0 wt% to about 20 wt%, about 0 wt% to about 10 wt%, about 0 wt% to about 5 wt%, about 0.001 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, about 5 wt% to about 15 wt%, or about 0.1 wt% to about 10 wt%, of the monomer mixture.

[0216] Exemplary cross linkers suitable for used in the monomer mixture further comprises alkyl glycol crosslinking agent having two or more ethylenically unsaturated reactive group, e.g., ethylene glycol di(met)acrylate, diethylene glycol di(meth)late, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di (meth)acrylate, nepentyl glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, or mixtures thereof.

[0217] In some embodiments, a cross linker described herein has a linear structure.

[0218] In some embodiments, a cross linker described herein has a branched (such as multi-arm) structure. In some embodiments, a cross linker described herein has a branched structure having two or more ethylenically unsaturated reactive group. In some embodiments, a cross linker described herein is an alkyl glycol crosslinking agent having two or more ethylenically unsaturated reactive groups. In some embodiments, a cross linker described herein comprises 2-6 ethylenically unsaturated reactive groups.

[0219] Other Monomers

[0220] In some embodiments, a siloxane-containing polymer described herein is a polymerization product of a monomer mixture, wherein the monomer mixture comprises one or more additional monomers. In some embodiments, the monomer mixture comprises one or more hydrophilic monomers such as ethyleneglycol methacrylate (mono-penta). In some embodiments, the monomer mixture comprises one or more hydrophobic monomers. In some embodiments, the additional monomer is present in the monomer mixture in an amount of about 0.001 wt% to about 50 wt%. In some embodiments, the additional monomer is present in the monomer mixture in an amount of about 0.001 wt% to about 25 wt%. In some embodiments, the additional monomer is present in the monomer mixture in an amount of about 0.001 wt% to about 15 wt%. In some embodiments, the additional monomer is present in the monomer mixture in an amount of less than 10 wt%. In some embodiments, the additional monomers comprise reactive moieties such as allyl, vinyl, acrylate or methacrylate. In some embodiments, the additional monomers comprises a linear monomer. In some embodiments, the additional monomers comprises a brunched monomer. In some embodiments, the additional monomers comprises a cyclic monomer. In some embodiments, the additional monomers comprises a monomer having a molecular weight of 25 to 50. In some embodiments, the additional monomers comprises a monomer having a molecular weight of 30 to 80. In some embodiments, the additional monomers comprises a monomer having a molecular weight of 50 to 200. In some embodiments, the additional monomers comprises a monomer having a molecular weight of 10 to 300. In some embodiments, the additional monomers comprises a monomer having a molecular weight of 100 to 500.

[0221] In some embodiments, the additional monomers comprises a rigid gas permeable contact lens-forming monomer.

[0222] Additives and Initiators

[0223] In some embodiments, the monomeric mixtures to be polymerized may further comprise various additives such as an antioxidant, coloring agent, ultraviolet absorber, lubricant internal wetting agents, toughening agents and the like and other constituents as is well known in the art. In some embodiments, the coloring agent is reactive. In some embodiments, the coloring agent is not reactive. In some embodiments, the coloring agent is an inorganic material. In some embodiments, the coloring agent is an organic material.

[0224] In some embodiments, a siloxane-containing polymer described herein is a polymerization product of a monomer mixture, wherein the monomer mixture comprises one or more initiators. In some embodiments, a siloxane-containing polymer described herein is a polymerization product of a monomer mixture, wherein the monomer mixture comprises one or more additives. The monomer mixture to be polymerized may further comprise various additives such as an antioxidant, coloring agent, ultraviolet absorber, lubricant internal wetting agents, toughening agents and the like and other constituents as is well known in the art.

[0225] In some embodiments, the monomer mixture comprises one or more UV blocking agents, one or more blue blocker agents, or a combination thereof. Any known UV blocker or later developed UV blocker are contemplated for use herein.

[0226] In some embodiments, one or more UV blocking agents and one or more blue blocker agents are present in an amount of about 0 to 2.5 wt% of the monomer mixture. In some embodiments, one or more UV blocking agents and one or more blue blocker agents are present in an amount of about 0 to 1 wt% of the monomer mixture.In some embodiments, one or more UV blocking agents and one or more blue blocker agents are present in an amount of about 0 to 0.1 wt% of the monomer mixture.

[0227] Representative examples of free radical thermal polymerization initiators include organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tertiarylbutyl peroxypivalate, peroxydicarbonate, and the like and azo compounds such as 2,2′-azobisisobutyronitrile (AIBN), 1,1′-azobis(cyclohexanecarbonitrile), 4,4′-azobis(4-cyanovaleric acid), and the like. Representative UV initiators are those known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocure® 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure® 651 and 184 (Ciba-Geigy), 2,2′Azobis(2-methylpropionitrile) (VAZO 64) and the like. In some embodiments, the initiator(s) will be employed in the monomer mixture at a concentration of about 0.01 to about 5 percent by weight of the total mixture.

[0228] In some embodiments, the one or more initiators comprise an Azo thermal initiator. Exemplary Azo thermal initiator include Azo nitrile (e.g., V-70, V65, AIBN, V-59, and V-40), Azo ester (e.g., V-601), and Azo amide (e.g., VAm-110).

[0229] In some embodiments, the one or more initiators comprise an epoxide thermal initiators. Exemplary epoxide thermal initiators include luperox 256, luperox 26 and benzoyl proxide.

[0230] Table 5. ExemplaryUV blocking agentsNameStructureBHPEA2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate 2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate HMBP2-Hydroxy-4-methacryloxybenzophenone BZEMA2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole Polymerization of Monomer Mixture

[0231] Siloxane-containing polymers described herein are polymerization product of monomers mixtures. Polymerization of suitable siloxane-based monomeric reagents yields polymer networks with rigid backbones (network strands) and percolated polymer fractions with high oxygen solubility that form polymeric materials with high hardness, modulus, toughness, and ultrahigh oxygen permeability without using PFAS. Monomer mixtures described herein can be polymerized to form network using thermally or photo-activated polymerization reactions under any inert gas positive pressure.

[0232] In one aspect, described herein is a material comprising the siloxane-containing polymer as described herein. In one aspect, described herein is a method of making a siloxane-containing polymer, wherein the method comprises polymerizing the monomer mixture. In one aspect, described herein is a method of making a material comprising the siloxane-containing polymer as described herein, wherein the method comprises polymerizing the monomer mixture. In some embodiments, the polymer is manufactured by in situ. In some embodiments, the polymer is manufactured by a solvent-free process. In some embodiments, the method further comprises one or more additives (e.g.., dyes, UV blockers, blue blocker reagent). In some embodiments, the method comprises curing such as thermal curing or photo curing. In some embodiments, the method comprises solvent-free polymerization. In some embodiments, the method comprises molding (e.g,. molding using casting and injection). In some embodiments, the method comprises molding in a mold. In some embodiments, the mold is a thermoplastic, thermosets, or silicon rubber. In some embodiments, the mold is has a rod shape. In some embodiments, the mold is has a button shape. In some embodiments, the mold has a base curvature (e.g., flat and curved). In one aspect, a monomer mixture described herein comprise active or non-active additives. In one aspect, a monomer mixture described herein comprise non-active additives, which is present in the resultant material that comprises the polymer. In one aspect, a material described herein comprise active or non-active additives (e.g., non-active coloring agent), in addition to the polymer composition.

[0233] The resulting cured PFAS-free materials have high hardness and hyper Dk values and demonstrate high affinity to the oxygen as required for high DK contact lenses. In some embodiments, depending on fractions of monomers in the formulation, the hardness of produced materials can be higher than 70 (shore D) up to 80 and Dk value is from 130 up to 200. Polymerization can be conducted thermally from 50 to 150 °C under a controlled temperature profile and inert gas pressure from few pascals to several mega pascals. Rigidity of polymer backbone using monomers with high Tg and having intra monomers interaction and percolation of siloxane polymer fractions lead to hyper oxygen permeabilities.

[0234] Polymerization may be facilitated by exposing a monomer mixture of the one or more cationic initiators comprising one or more polymerizable groups and the alkyl-substituted oxazoline together with, optionally, the one or more cross linkers and / or one or more hydrophilic monomers and / or protected hydrophilic monomers, to heat and / or radiation, such as ultraviolet light, visible light, or high energy radiation. A polymerization initiator may be included in the monomer mixture to facilitate the polymerization step.

[0235] Polymerization can be performed in a reaction medium, such as, for example, a solution or dispersion using a solvent, e.g., water or an alkanol containing from 1 to 4 carbon atoms such as methanol, ethanol or propan-2-ol. In some embodiments, a mixture of any of the above solvents may be used.

[0236] In some embodiments, polymerization is carried out for about 15 minutes to about 72 hours, and under an inert atmosphere of, for example, nitrogen or argon. In some embodiments, the resulting polymerization product can be dried under vacuum, e.g., for about 5 to about 72 hours or left in an aqueous solution prior to use.

[0237] Polymerization can be conducted under inert gas blanket from a few pascal to mega pascal using thermal or photo initiators and adding of UV and Blue light blocker (in case of demand) without using and PFAS monomers. In one aspect, it is discovered that using monomers that form rigid backbone and having dynamic interaction between polymerized monomer in the polymer chain and higher percentage of siloxane in the monomer mixture can increase free volume and rigidity of materials and formation of percolated siloxane domains in a polymer network that are suitable for preparation of hyper DK PFAS-free materials.

[0238] In accordance with a further aspect of the present disclosure, a method of producing an hyper Dk materials; comprises contacting and reacting: low Tg to medium Tg siloxane materials such as 3-methacryloyloxypropyl tris(trimethylsiloxy)silane, N-(3-(3-(1,1, 1, 5, 5, 5-Hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)methacrylamide, product of reaction between isocyano alkyl (meth)acrylate or (meth)acrylamide with 3-(1,1, 1, 5, 5, 5-Hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propan-1-amine or 3-(1,1, 1, 5, 5, 5-Hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl alcohol; 1,1, 1, 5, 5, 5-Hexamethyl-3-((trimethylsilyl)oxy)-3-(4-vinylphenyl)trisiloxane; and styrylethyltris(trimethylsiloxy)silane and high Tg hydrophilic monomers such as methacrylic acid, and any high Tg cyclic monomers and high Tg hydrophobic monomers such as mono, bi and tri alkyl (methyl) styrene, adamantyl metacrylate and without imitation thereto. In addition to siloxane cross linkers, any alkyl glycol di methacrylamide or di methacrylate such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and pentaerythritol tetramethacrylate and not limited to are used for cross linking and increase the modulus and hardness of polymer network. These monomer mixtures can be cured under inert gas positive pressure up to several mega pascal using thermal initiators with activation temperature from 25 C to 150 C such as peroxide (Benzoyl peroxide, Luperox 26 and 256), Azo initiators such as AIBN or using light (high energy to low energy) and photo initiator such as BPO, Irgacure 819 but not limited to. The hardness of these materials can be controlled by the percentage of high Tg monomers and the DK number is dependent on the rigidity of polymer backbone and the percentage of siloxane monomer and the status of siloxane domain percolation.

[0239] The polymerization can be conducted in the tubes to make rods or between glass sheets to make polymer sheets and buttons shape molds with both flat surface or one flat and one curved surface. The polymerization vessel can be under positive inert gas such as nitrogen, argon, helium from few pascal to several mega pascal. The buttons and rods can have diameter from 7 mm to 25 mm in different color such as blue, ice blue, Green, purple, but not limited to. In the monomer mixture, UV and blue blocker may be used to make Class I and II in terms of UV blocking lenses.

[0240] OPHTHALMIC DEVICE

[0241] In one aspect, disclosed herein is an ophthalmic device comprising a siloxane-containing polymer of the present disclosure. In some embodiments, the ophthalmic device is a contact lens, an intraocular lens, or a corneal implant. In some embodiments, the ophthalmic device is a contact lens. In some embodiments, the ophthalmic device is an extended wear lens.

[0242] In some embodiments, the ophthalmic device has a Dk number of at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, or at least 200. In some embodiments, the ophthalmic device has a Dk number of at least 30. In some embodiments, the ophthalmic device has a Dk number of at least 40. In some embodiments, the ophthalmic device has a Dk number of at least 50. In some embodiments, the ophthalmic device has a Dk number of at least 60. In some embodiments, the ophthalmic device has a Dk number of at least 70. In some embodiments, the ophthalmic device has a Dk number of at least 80. In some embodiments, the ophthalmic device has a Dk number of at least 90. In some embodiments, the ophthalmic device has a Dk number of at least 100. In some embodiments, the ophthalmic device has a Dk number of at least 110. In some embodiments, the ophthalmic device has a Dk number of at least 120. In some embodiments, the ophthalmic device has a Dk number of at least 130. In some embodiments, the ophthalmic device has a Dk number of at least 140. In some embodiments, the ophthalmic device has a Dk number of at least 150. In some embodiments, the ophthalmic device has a Dk number of at least 160. In some embodiments, the ophthalmic device has a Dk number of at least 170. In some embodiments, the ophthalmic device has a Dk number of at least 180. In some embodiments, the ophthalmic device has a Dk number of at least 190. In some embodiments, the ophthalmic device has a Dk number of at least 200. In some embodiments, the ophthalmic device has a Dk number of at least 210. In some embodiments, the ophthalmic device has a Dk number of at least 220. In some embodiments, the ophthalmic device has a Dk number of at least 230. In some embodiments, the ophthalmic device has a Dk number of at most 240. In some embodiments, the ophthalmic device has a Dk number of at most 220. In some embodiments, the ophthalmic device has a Dk number of at most 210. In some embodiments, the ophthalmic device has a Dk number of at most 200. In some embodiments, the ophthalmic device has a Dk number of at most 190. In some embodiments, the ophthalmic device has a Dk number of at most 180. In some embodiments, the ophthalmic device has a Dk number of at most 170. In some embodiments, the ophthalmic device has a Dk number of at most 160. In some embodiments, the ophthalmic device has a Dk number of at most 150. In some embodiments, the ophthalmic device has a Dk number of about 100 to 200. In some embodiments, the ophthalmic device has a Dk number of about 100 to 150. In some embodiments, the ophthalmic device has a Dk number of about 150 to 200. In some embodiments, the ophthalmic device has a Dk number of about 180 to 220.

[0243] In some embodiments, the ophthalmic device has a Shore D hardness of at least 70. In some embodiments, the ophthalmic device has a Shore D hardness of at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75. In some embodiments, the ophthalmic device has a Shore D hardness of about 70-80. In some embodiments, the ophthalmic device has a Shore D hardness of about 65-85.

[0244] The ophthalmic devices described herein advantageously provide for increased oxygen permeability and therefore, improved comfort. In some embodiments, the ophthalmic devices described herein are intended for direct contact with body tissue or body fluid. In some embodiments, the term “ophthalmic device” refers to devices that reside in or on the eye. These devices can provide optical correction, wound care, drug delivery, diagnostic functionality or cosmetic enhancement or effect or a combination of these properties. Useful ophthalmic devices include, for example, ophthalmic lenses such as soft contact lenses, e.g., a soft, hydrogel lens, soft, non-hydrogel lens and the like, hard contact lenses, e.g., a hard, gas permeable lens material and the like, intraocular lenses, overlay lenses, ocular inserts, optical inserts and the like.

[0245] The ophthalmic devices described herein, e.g., contact lenses or intraocular lenses, can be prepared by polymerizing the herein described monomer mixtures to form a product that can be subsequently formed into the appropriate shape by, for example, lathing, injection molding, compression molding, cutting and the like. For example, in producing contact lenses, the initial mixture may be polymerized in tubes to provide rod-shaped articles, which are then cut into buttons. The buttons may then be lathed into contact lenses.

[0246] The ophthalmic devices can be made by any suitable means. In some embodiments, the ophthalmic devices such as contact lenses may be cast directly in molds, e.g., polypropylene molds, from the mixtures, e.g., by spincasting and static casting methods. In some embodiments, the ophthalmic devices such as contact lenses may be made by 3D printing.

[0247] The ophthalmic devices such as contact lenses obtained herein may be subjected to optional machining operations. For example, the optional machining steps may include buffing or polishing a lens edge and / or surface. In some embodiments, such machining processes may be performed before or after the product is released from a mold part, e.g., the lens is dry released from the mold by employing vacuum tweezers to lift the lens from the mold, after which the lens is transferred by means of mechanical tweezers to a second set of vacuum tweezers and placed against a rotating surface to smooth the surface or edges. The lens may then be turned over in order to machine the other side of the lens. In some embodiments, the lens may then be transferred to individual lens packages containing a buffered saline solution. The saline solution may be added to the package either before or after transfer of the lens. Appropriate packaging designs and materials are known in the art. A plastic package is releasably sealed with a film. Suitable sealing films are known in the art and include foils, polymer films and mixtures thereof. The sealed packages containing the lenses are then sterilized to ensure a sterile product. Suitable sterilization means and conditions are known in the art and include, for example, autoclaving. As one skilled in the art will readily appreciate other steps may be included in the molding and packaging process described above. Such other steps can include, for example, coating the formed lens, surface treating the lens during formation (e.g., via mold transfer), inspecting the lens, discarding defective lenses, cleaning the mold halves, reusing the mold halves, and the like and combinations thereof.

[0248] In one aspect, the disclosure relates to hyper gas-permeable PFAS-free materials, products comprising the materials, and methods of making.

[0249] Although the invention has been described with reference to preferred embodiments thereof, it is understood that various modifications and using other high Tg monomers may be made thereto without departing from the full spirit and scope of the invention as defined by the claims which follow.EXAMPLES

[0250] Although the invention has been described with reference to preferred embodiments thereof, it is understood that various modifications and using other high Tg monomers may be made thereto without departing from the full spirit and scope of the invention as defined by the claims which follow.

[0251] In order that the invention described herein may be more fully understood, the following examples are set forth. The examples described in this application are offered to illustrate the monomers, formulations, polymer materials, and methods provided herein and are not to be construed in any way as limiting their scope.

[0252] It is understood that, unless indicated otherwise, the values presented in the examples are approximate values, and are subject to experimental and instrumental variations.

[0253] Example 1. Materials and Methods

[0254] Mechanical properties (modulus, strength, and toughness) were measured by a dynamic mechanical analyzer (DMA) from TA Instruments operating in a tensile mode according to the ASTM 638-22 standards. The test sample dimensions conform to the Type IV specimens prepared by die cutting. Tensile tests were conducted at ambient conditions (T=23 ± 2°C, RH=50 ± 5%) at different strain rates ranging from 0.001 to 10 s-1to ensure equilibrium properties. Five samples were measured in triplicates (total 15 measurements) to verify reproducibility.

[0255] Indentation hardness was measured by a Vickers hardness tester according to the ASTM D2240-15 standard. Flat 2″ X 2″ specimens of 1 mm thickness were placed on a hard flat surface followed by pressing an indentor into the specimen. Five samples were measured in triplicates to ensure reproducibility. The hardness numbers were evaluated using the Shore D scale. The indentation tests were conducted at ambient conditions (T=23 ± 2°C, RH=50 ± 5%). Five samples were measured in triplicates (total 15 measurements) to verify reproducibility.

[0256] The oxygen permeability was measured for a set of films of different thicknesses ranging from 100 to 500 micrometers using the Coulometric Method according to the ISO 9913 testing standard, which closely matches the ASTM D3985 standard. The oxygen permeability index was evaluated in Dk. Oxygen permeability instrument was calibrated using a reference film before testing to determine the calibration factor of the instrument. Testing temperature was maintained at 23 ± 2°C. In certain embodiments, testing temperature of specimens was set to 35 ± 2°C to model the human eye environment.

[0257] Example 2. Polymer Composition and Synthesis

[0258] The following polymers Examples 1-85 were made and tested according to the composition shown in Tables E1 and E2. The curing profile is described in Example 3.

[0259] Reactions were conducted under inert gas pressure from a few Pascal (atmospheres: 1atm~0.1 MPa) to about 10 MPa using heat from 40 °C to 150 °C or light with wavelengths, ranging from low to high energy wavelengths.

[0260] The mixture of chemicals was shaken (stirred) for 30 minutes to make it homogeneous and then filtered using 0.22 um PTFE syringe filter to the button, rod or sheet mold. The polymerization was conducted under a well-defined (controlled) temperature profile or light intensity profile under inert gas pressure from a few pascals to several mega pascal.

[0261] Siloxane monomers were mixed with other high Tghydrophilic and hydrophobic monomers (as provided in Tables E1 and E2) such as methacrylic acid, mono, bi, tri methyl styrene, adamantyl methacrylate, isobronyl methacrylate but not limited to these and cross linkers such as alkyl glycol dimethacrylate such as di ethylene or neopentyl glycol dimethacrylate and difunctional polysiloxane x-linker. The thermal or photo initiator, UV and blue light blocker, and color tint were added and degassed using inert gas pressurizing and vacuum several cycles. The mixture was kept under positive pressure of inert gas from a few pascal to MPas to have suitable and healthy thermal or photo polymerization under temperature profile or light intensity.

[0262] Table E1.Monomers / reagentsEX 1EX 2EX 3EX 4EX 5EX 6EX 7EX 8EX 9EX 10EX 11TrisMA68.465.3868.6866.7064.8396865703955Tris methacylamide-5.42--5.54----TrisUrea----------3418Neopentyl glycol dimethacrylate(NGDMA)1110.24119.510.291111101187Methacrylated polydimethylsiloxane5.85.135.485.75.1565.865.577Me3 styrene--9.987.2----7.521Tris styrene9.959.32-4.769.4439910000Methacrylic acid4.724.444.746.194.68579755Adamantyl methacrylate---------23Isobronyl methacrylate---------34UV blocker0.40.40.40.40.40.40.40.40.40.40.4Blue blocker reagent0000000.10.10.10.20.2initiator0.10.10.10.10.10.10.10.10.10.10.1Harness shore D7372767571747574767475Dk number192158135145160198192195162193188Modulus (MPa)14001500160015701500145014801430157015401580Toughness (MNm / m3)2.42.8Curing conditionTable E1 cont’dMonomers / reagentsEX 12EX 13EX 14EX 15EX 16EX17EX 18EX 19EX 20EX 21EX 22TrisMA6465.3868.6866.7064.868.468.468.448.448.455Tris methacylamide-5.42--5.54----monomethacryloxypropyl terminated polydimethylsiloxane----------3.4TrisUrea---------202010Neopentyl glycol dimethacrylate(NGDMA)11.110.24119.510.29111111101010Methacrylated polydimethylsiloxane4.55.135.485.75.155.85.85.85.85.85.8Me3 styrene (2, 4 , 6 trimethylstyrene)16.8-9.987.2---4.725--Tris styrene9.32-4.769.449.959.959.959.959.959.95Methacrylic acid3--4.68-----Adamantyl methacrylate-4.444.74-6.19--4.724.72--05.72Isobronyl methacrylate---------00Initiator0.10.10.10.10.10.10.10.10.10.10.1UV blocker0.40.40.40.40.40.40.40.40.40.40.4Blue blocker reagent0000000.10.10.10.20.2Harness shore D75747874727476745747572Dk number196155137140167189198192172189205Modulus (MPa)15001600155014801650155016501560159016001680Toughness (MNm / m3)-3.1Table E2.Ex 21EX 22Ex 23Ex 24Ex 25Ex 26Ex 27Ex 28Ex 29Ex 30Ex 31Ex 32Ex 33TRISMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)68.2765.567.9665.9767.0148.1548.3719.4448.3668.2765.548.3668.27TRISNMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide)19.7519.819.8TRISUREMA (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylate4.7319.5219.7948.194.73Ethyleneglycol methacrylate (mono-penta)11.0511.05Neopentyldimethacrylate11.0210.3310.899.5811.0210.219.99.69.910.339.9monomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M12monomethacrylamido terminated polydimethylsiloxanepolydimethylsiloxane dimethacrylate5.155.15polydimethylsiloxane dimethacrylamide5.465.765.725.865.895.726.735.725.465.725.462, 4 , 6 trimethylstyrene10.037.126.765.755.811010tris Styrene (styrylethyltris(trimethylsiloxy)silane)9.359.894.88.839.959.964.99.969.359.96methacrylic acid5.724.71adamantyl methacrylate4.714.5456.295.724.785.724.71isobrony / e methacrylate4.54AIBN VAZO 67Luporox 26 / 2560.060.070.0630.0610.0680.0640.0640.0640.0640.060.070.0640.06UV blocker0.440.340.440.4580.4510.470.480.4460.480.440.440.480.44blue light blockerCuring profileProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 1- BProfile 1- AHardness767272757374737373Dk132195190158152145ModulusTable E2 cont’dEx 34Ex 35Ex 36Ex 37Ex 38Ex 39Ex 40Ex 41Ex 42Ex 43Ex 44Ex 45Ex 46Ex 47Ex 48TRISMA, (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)65.543.3663.2759.6868.2565.567.9665.956748.1548.3719.4568.2767.9667.96TRISNMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide)19.8TRISUREMA (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylate4.734.744.7319.519.7548.2Ethyleneglycol methacrylate (mono-penta)11.05Neopentyldimethacrylate10.339.910.331110.3310.859.551110.29.99.61110.8910.89monomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M122.452.53.05monomethacrylamido terminated polydimethylsiloxane2.552.52.65polydimethylsiloxane dimethacrylate5.155.155.15polydimethylsiloxane dimethacrylamide5.725.465.55.75.75.855.855.76.75.455.765.762, 4 , 6 trimethylstyrene10107.16.755.755.810Tris Styrene (Styrylethyltris(trimethylsiloxy)silane)9.359.969.359.39.894.88.89.959.954.99.99.9Methacrylic acid4.545Adamantyl methacrylate5.724.714.654.556.35.74.754.75Isobrony / e methacrylate4.54AIBN VAZO 670.150.150.150.150.150.150.150.150.10.10.1Luporox 26 / 2560.070.0640.060.070.060.060.06UV blocker0.440.480.440.440.440.340.440.450.450.470.480.450.440.440.44blue light blockerCuring profileProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProflie 2-CHardness75737174727472767272Dk135187195ModulusTable E2 cont’dEx 49Ex 50Ex 51Ex 52Ex 53Ex 54Ex 55Ex 56Ex 57Ex 58Ex 59Ex 60Ex 61Ex 62Ex 63TRISMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)67.9565.9565.9565.56748.1567.9567.9538.9367.9567.9521.538.9367.9567.95TRISNMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide)21.5TRISUREMA (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylate4.719.5Ethyleneglycol methacrylate (mono-penta)10.85Neopentyldimethacrylate10.859.559.55101110.210.8510.8510.8510.89a10.8510.8910.85b10.85cmonomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M12monomethacrylamido terminated polydimethylsiloxanepolydimethylsiloxane dimethacrylatepolydimethylsiloxane dimethacrylamide5.75.75.75.155.855.855.75.75.75.75.765.75.765.765.72, 4 , 6 trimethylstyrene57.113.46.755.7555555555Tris Styrene (Styrylethyltris(trimethylsiloxy)silane)9.94.84.89.358.89.929.99.938.929.99.934.8538.829.99.9Methacrylic acid5Adamantyl methacrylate4.54Isobrony / e methacrylate6.321.5AIBN VAZO 670.10.10.10.10.10.10.10.10.10.10.10.10.10.10.1Luporox 26 / 2560.060.060.060.060.060.060.060.060.060.060.060.060.060.060.06UV blocker0.440.440.450.340.440.470.440.440.440.440.440.440.440.440.44blue light blockerCuring profileProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CProfile 2-CHardness727575747374727274737273727373Dk190165160195148146187190210185195205210194190ModulusTable E2 cont’dEx 64Ex 65Ex 66Ex 67Ex 68Ex 69Ex 70Ex 71Ex 72Ex 73Ex 74Ex 75Ex 76TRISMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)6463646464555568.3668.3668.3647.1468.3668.36TRISNMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide)TRISUREMA (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylateEthyleneglycol methacrylate (mono-penta)11Neopentyldimethacrylate1112111111111111111111b11cmonomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M1210 (M11)10 (M11 amide)monomethacrylamido terminated polydimethylsiloxanepolydimethylsiloxane dimethacrylatepolydimethylsiloxane dimethacrylamide55555445.815.815.815.815.815.812, 4 , 6 trimethylstyrene19.54-4.714.714.714.714.71Tris Styrene (Styrylethyltris(trimethylsiloxy)silane)9.99.931.439.99.9Methacrylic acid19.4519.4519.454.71Adamantyl methacrylate19.549.54Isobrony / e methacrylate19.5410AIBN VAZO 670.150.150.150.20.20.20.20.20.2Luporox 26 / 2560.060.060.060.0600.00.000.00.020.020.020.020.020.02UV blocker0.40.40. 40.40.40.40.40.4e0.4e0.4e0.4e0.4e0.4eblue light blockerCuring profileProfile 1- AProfile 1- AProfile 1- AProfile 1- AProfile 2-CProfile 2-CProfile 2-CProfile 3-DProfile 3-DProfile 3-DProfile 3-DProfile 3-DProfile 3-DHardness747374747574737373Dk11010598100102195ModulusTable E2 cont’dEx 77Ex 78Ex 79Ex 80Ex 81Ex 82TRISMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)68.3668.3668.3647.1468.3647.14TRISNMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide)TRISUREMA (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylateEthyleneglycol methacrylate (mono-penta)Neopentyldimethacrylate3.937.867.867.867.867.86monomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M12monomethacrylamido terminated polydimethylsiloxanepolydimethylsiloxane dimethacrylatepolydimethylsiloxane dimethacrylamide5.815.815.815.815.815.812, 4 , 6 trimethylstyrene11.787.867.867.86Tris Styrene (Styrylethyltris(trimethylsiloxy)silane)9.99.99.931.339.931.33Methacrylic acid7.867.86Adamantyl methacrylateIsobrony / e methacrylateAIBN VAZO 670.20.20.20.20.20.2Luporox 26 / 2560.020.020.020.020.020.02UV blocker0.4e0.4e0.4e0.4e0.4e0.4eblue light blockerCuring profileProfile 3-DProfile 3-DProfile 3-DProfile 3-DProfile 3-DProfile 3-DHardness7675737575Dk185190Modulusa= 1, 3 glyceryl dimethacrylate

[0263] b= 1,4 butanodiol di methacrylate

[0264] c= diethyleneblycol dimethacrylate

[0265] e= Over than 100 wt%

[0266] Table E2 cont’dEx 82Ex 83Ex 84Ex 85TRISMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)68.466.3769.7665.40TRISNMA (3-[Tris(trimethylsiloxy)silyl]propyl methacrylamide)TRISUREMA (3-[Tris(trimethylsiloxy)silyl]propyl isociano ethyl methacrylateEthyleneglycol methacrylate (mono-penta)Neopentyldimethacrylate11.029.439.929.17monomethacryloxy terminated polydimethylsiloxane (MCR-M07 / M11 / M12monomethacrylamido terminated polydimethylsiloxanepolydimethylsiloxane dimethacrylatepolydimethylsiloxane dimethacrylamide5.465.700.05.622, 4 , 6 trimethylstyrene7.344.620.03.64Tris Styrene (Styrylethyltris(trimethylsiloxy)silane)04.7412.899.71Methacrylic acid7.348.726.986.08Adamantyl methacrylateIsobrony / e methacrylateAIBN VAZO 670.10.10.10.1Luporox 26 / 2560.020.020.0200.02UV blocker0.330.320.330.32blue light blockerCuring profileProfile 3-DProfile 3-DProfile 3-DProfile 3-DHardness77767374.5Dk135178252197Modulusa= 1, 3 glyceryl dimethacrylate

[0267] b= 1,4 butanodiol di methacrylate

[0268] c= diethyleneblycol dimethacrylate

[0269] e= Over than 100 wt%

[0270] Certain structures of monomers used in the polymerization of Ex 1-Ex 63 are illustrated below in Table E3.

[0271] Table E3. Exemplary Monomers Used in Ex1-Ex63.NameStructureStructureTrisMA3-[Tris(trimethylsiloxy)silyl]propylmethacrylate Tris methacylamide (TRISNMA)3-methacrylamidopropyltris(trimethylsiloxy)silane TrisUrea Neopentyl glycol dimethacrylateNGDMA Methacrylated polydimethylsiloxanemethacryloxypropyl terminated polydimethylsiloxaneDMS-R18 (ester or amide) Mn=3000Me3 styrene2, 4, 6 trimethyl styrene Tris styrenestyrylethyltris(trimethylsiloxy)silane Methacrylic acid Adamantyl methacrylate Isobronyl methacrylate UV blocker2-(4-Benzoyl-3-hydroxyphenoxy)ethyl methacrylate (UV 416 )2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (SA monomer)

[0272] Example 3. Curing Profiles

[0273] 1. Initiator with high activation temperature

[0274] a) Slow cure: under nitrogen pressure (after degassing cycles (vacuum / N2 fill)Temp CTime (hour)250-125 to 50 ramp0-150-650-1655-1065 to 800-180 to 950-1955-1095 to 1100-11100-10110 to 252-5b) Fast cure: under nitrogen pressure (after degassing cycles (vacuum / N2 fill)Temp CTime (hour)250-125 to 950-29510-1695 to 1100-11108-10110 to 252-5Initiator with low activation temperature. c) Slow cure: under nitrogen pressure (after degassing cycles (vacuum / N2 fill)Temp CTime (hour)250-125 to 45 ramp0-14510-7245 to 550-155 to 650-16510-7265 to 252-10c-1) Option 1 (Cont.)Temp CTime (hour)65 to 950-2951-1095 to252-10c-2) Option 2 (Cont.)Temp CTime (hour)95 to 1100-211010-24110 to252-103. Mixture of Initiator with low and high activation temperature

[0275] d. Slow cure: under nitrogen pressure (after degassing cycles (vacuum / N2 fill)Temp CTime (hour)250-125 to 400-14010-7240 to 65 ramp0-1655-1065 to 800-180 to 950-1955-1095 to 1100-11100-10110 to 252-6

Claims

1.A material for ophthalmic device, comprising a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising:one or more high Tg cross linkers;one or more high Tg monomers; andone or more siloxane-containing monomers;wherein the siloxane-containing polymer has a Dk number of at least 45.2.The material of claim 1, wherein the siloxane-containing polymer comprises a percolation structure.3.The material of claim 1, wherein the percolation structure exceeds a percolation threshold.4.The material of any one of claims 1 to claim 3, wherein the siloxane-containing polymer is substantially free of PFAS material.5.A material for ophthalmic device comprising a siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising:one or more high Tg cross linkers;one or more high Tg monomers; andone or more siloxane-containing monomers;wherein the siloxane-containing polymer comprises a percolation structure (optionally, percolation structure that exceeds a percolation threshold).6.The material of claim 5, wherein the siloxane-containing polymer is substantially free of PFAS material.7.The material of any one of claims 2 to 6, wherein the percolation structure are percolated channels.8.The material of claim 7, wherein the percolated channels of siloxane-rich material (component) are formed upon microphase separation of the siloxane-containing polymer.9.The material of claim 7, wherein the percolated channels are formed upon microphase separation of the siloxane-containing polymer.10.The material of any one of claims 7 to 9, wherein the microphase separation generates domains in the polymer structure that they percolate and make channels for better permeability to oxygen.11.The material of any one of claims 2 to 9, wherein exceeding the percolation threshold significantly facilitates the permeation (transmission) of oxygen through an optical device material.12.The material of any one of claims 2 to 11, wherein the percolation threshold is sufficient to allow the permeation of oxygen.13.The material of any one of claims 1 to 12, wherein the one or more siloxane-containing monomers comprise one or more bulky siloxane monomers.14.The material of claim 13, wherein the one or more bulky siloxane monomers comprise Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane, or a combination thereof.15.The material of any one of claims 1 to 14, wherein the one or more siloxane-containing monomers comprise one or more linear siloxane monomers.16.The material of claim 15, wherein the one or more linear siloxane monomers comprise monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, or a combination thereof.17.The material of any one of claims 1 to 12, wherein the one or more siloxane-containing monomers comprise Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane, monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, or a combination thereof.18.The material of any one of claims 1 to 12, wherein the one or more siloxane-containing monomers comprisea) a monomer of Formula (I) (I),whereinR1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;Y is -O-, -S- or -NH-;X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,n is an integer number selected from 0 to 100; andm is an integer number selected from 0 to 100,b) a monomer of Formula (II) (II),wherein n is an integer number selected from 0 to 100,orc) a monomer of Formula (III), (III),wherein:R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;Y is -O-, -S- or -NH-;X is -O-, -S- , -NH-C=O-O- or -NH-C=O=NH- or -NH- ;m is an integer number selected from 0 to 100;n is an integer number selected from 0 to 100; andI is an integer number selected from 0 to 100,or a combination thereof.19.The material of any one of claims 1 to 12, wherein the one or more siloxane-containing monomers comprisea) a monomer of Formula (I*), (I*),wherein:R1is hydrogen or C1-C3alkyl;each R2is independently C1-C4alkyl;Y is -O-, -S- or -NH-;X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,n is an integer number selected from 0 to 100; andm is an integer number selected from 0 to 100,b) a monomer of Formula (II*) (II*),wherein:n is an integer number selected from 0 to 100; andeach R3is independently C1-C4alkyl,orc) a monomer of Formula (III*) (III*),wherein:R1is hydrogen or C1-C3alkyl;Y is -O-, -S- or -NH-;X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH- ;each R4is independently C1-C4alkyl;m is an integer number selected from 0 to 100;n is an integer number selected from 0 to 100; andI is an integer number selected from 0 to 100,or a combination thereof.20.The material of any one of claims 1 to 12,wherein the one or more siloxane-containing monomers comprise one or more monomers from Tables 1 and 2.21.The material of any one of claims 1 to 12, wherein the one or more siloxane-containing monomers comprise TRISMA, TRISNMA, TRISUREMA or any combination thereof.22.The material of any one of claims 1 to 21, wherein the one or more siloxane-containing monomers comprise an amide functional group, a urea functional group, an aryl group (such as phenyl or benzyl), or a combination thereof.23.The material of claim 22, wherein the amide, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain).24.The material of any one of claims 1 to 23, wherein the one or more siloxane-containing monomers comprise a branched (including multi-armed structures) or linear monomer, and optionally contain a cyclic ring.25.The material of any one of claims 1 to 24, wherein the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 5 wt% to about 98 wt% of the monomer mixture.26.The material of any one of claims 1 to 24, wherein the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 30 wt% to about 95 wt% of the monomer mixture.27.The material of any one of claims 1 to 24, wherein the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 50 wt% to about 90 wt% of the monomer mixture.28.The material of any one of claims 1 to 27, wherein the monomer mixture further comprises one or more siloxane-containing cross linkers.29.The material of claim 28, wherein the siloxane-containing cross linkers comprise a branched (including multi-armed structures) or linear cross linker, and optionally contain a cyclic ring.30.The material of claim 28 or 29, wherein the siloxane-containing cross linkers comprises one or more methacrylate- / acrylate-terminated polydimethylsiloxanes, or methacrylamide polydimethylsiloxane, or a combination thereof.31.The material of claim 28 or 30, wherein the siloxane-containing cross linkers comprises methacryloxypropyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated branched polydimethylsiloxane, (3-acryloxy-2-hydroxypropoxypropyl)-terminated polydimethylsiloxane, methacrylamido propyl polydimethylsiloxane, or a combination thereof.32.The material of claim 28 or 30, wherein the siloxane-containing cross linkers comprises methacylated poydimethylsiloxane.33.The material of any one of claims 28 to 32, wherein the one or more siloxane-containing cross linkers comprise one or more cross linkers selected from Table 4.34.The material of any one of claims 28 to 33, wherein the one or more siloxane-containing cross linkers comprise an amide functional group, a urea functional group, an aryl functional group (such as phenyl or benzyl), or a combination thereof.35.The material of claim 34, wherein the amide functional group, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain).36.The material of claim 34 or 35, wherein the presence of amide groups and aryl (e.g., benzyl) groups and urethane and urea group directly connected to the backbone functions to make some dynamic interaction such as π–π, HYDROGEN BONDING that increase rigidity of polymer chains backbone and consequently increases the stiffness, hardness and free volume that increase Dk value.37.The material of any one of claims 28 to 34, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of 0 wt% to about 50 wt% of the monomer mixture.38.The material of any one of claims 28 to 37, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0 wt% to about 30 wt% of the monomer mixture.39.The material of any one of claims 28 to 38, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0.01 wt% to about 50 wt% of the monomer mixture.40.The material of any one of claims 28 to 38, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 1 wt% to about 10 wt% of the monomer mixture.41.The material of any one of claims 28 to 38, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0.1 wt% to about 8 wt% of the monomer mixture.42.The material of any one of claims 1 to 41, wherein the one or more high Tg cross linkers have a Tg of at least 80oC.43.The material of any one of claims 1 to 41, wherein the one or more high Tg cross linkers have a Tg of at least 100oC.44.The material of any one of claims 1 to 41, wherein the one or more high Tg cross linkers have a Tg of at least 110oC.45.The material of any one of claims 1 to 44, wherein the one or more high Tg cross linkers comprise alkyl glycol dimethacrylate such as neopentyl glycol dimethacrylate.46.The material of any one of claims 1 to 44, wherein the one or more high Tg cross linkers comprise one or more cross linkers selected from Table 3.47.The material of any one of claims 1 to 46, wherein the the one or more high Tg cross linkers comprise a branched (including multi-armed structures) or linear cross linker, and optionally contain a cyclic ring.48.The material of any one of claims 1 to 47, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture.49.The material of any one of claims 1 to 47, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least about 5 wt% of the monomer mixture.50.The material of any one of claims 1 to 47, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, or at least 15 wt% of the monomer mixture.51.The material of any one of claims 1 to 50, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 50 wt% of the monomer mixture.52.The material of any one of claims 1 to 50, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture.53.The material of any one of claims 1 to 50, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture.54.The material of any one of claims 1 to 50, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most 25 wt%, at most 20 wt%, at most 18 wt%, at most 17 wt%, at most 16 wt%, at most 15 wt%, at most 14 wt%, at most 13 wt%, at most 12 wt%, at most 11 wt%, at most 10 wt% of the monomer mixture.55.The material of any one of claims 1 to 45 , wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture.56.The material of any one of claims 1 to 55, wherein the monomer mixture further comprises one or more additional cross linkers.57.The material of claim 56, wherein the one or more additional cross linkers comprise a branched (including multi-armed structures) or linear cross linker, and optionally contain a cyclic ring.58.The material of claim 56, wherein the one or more additional cross linkers or high Tg cross linkers, or both comprise an amide functional group, a urea functional group, an aryl functional group (such as phenyl or benzyl), or a combination thereof.59.The material of claim 58, wherein the amide functional group, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain).60.The material of any one of claims 1 to 59, wherein the one or more high Tg monomers have a Tg of at least 80oC.61.The material of any one of claims 1 to 59, wherein the one or more high Tg monomers have a Tg of at least 100oC.62.The material of any one of claims 1 to 59, wherein the one or more high Tg monomers have a Tg of at least 110oC.63.The material of any one of claims 1 to 62, wherein the one or more high Tg monomers comprise alkyl substituted styrene monomer, adamantyl derivative, Isobronyl derivative, methacrylate, methacrylamide, or a mixture thereof.64.The material of any one of claims 1 to 62, wherein the one or more high Tg monomers comprise isobornyl acrylate, methyl methacrylate, mono-, di-, tri-methyl styrene, adamantyl methacrylate, isobornyl methacrylate, or a mixture thereof65.The material of any one of claims 1 to 62, wherein the one or more high Tg monomers comprise methyl methacrylate, mono-, di-, tri-methyl styrene, adamantyl methacrylate, isobornyl methacrylate, or a mixture thereof.66.The material of any one of claims 1 to 65, wherein the one or more high Tg monomers comprise an amide functional group, a urea functional group, an aryl functional group (such as phenyl or benzyl), or a combination thereof.67.The material of claim 66, wherein the amide, urea functional group, or aryl functional group is within close proximity to the polymer backbone (e.g., not separated from the polymer backbone by more than 10, 6, 5, 4, or 3 non-H atoms on a linear chain)68.The material of any one of claims 1 to 67, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture.69.The material of any one of claims 1 to 67, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at least about 10 wt% of the monomer mixture.70.The material of any one of claims 1 to 67, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at least 5 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, or at least 50 wt% of the monomer mixture.71.The material of any one of claims 1 to 70, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture.72.The material of any one of claims 1 to 70, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture.73.The material of any one of claims 1 to 70, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 12 wt%, at most 10 wt%, or at most 5 wt% of the monomer mixture.74.The material of any one of claims 1 to 62, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture.75.The material of any one of claims 1 to 62, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of about 5 wt% to about 70 wt% of the monomer mixture.76.The material of any one of claims 1 to 75, wherein the monomer mixture further comprises one or more UV blocking agents, one or more blue blocker agents, or a combination thereof.77.The material of claim 77, wherein one or more UV blocking agents and one or more blue blocker agents are present in the monomer mixture in an amount of 0 to 1 wt% of the monomer mixture.78.The material of claim 77, wherein one or more UV blocking agents and one or more blue blocker agents are present in the monomer mixture in an amount of 0 to 0.1 wt% of the monomer mixture.79.The material of any one of claims 1 to 78, wherein the siloxane-containing polymer has a Dk number of at least 80.80.The material of any one of claims 1 to 78, wherein the siloxane-containing polymer has a Dk number of at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, or at least 200.81.The material of any one of claims 1 to 78, wherein the siloxane-containing polymer has a Dk number of at most 350.82.The material of any one of claims 1 to 79, wherein the siloxane-containing polymer has a Shore D hardness of at least 50.83.The material of any one of claims 1 to 82, wherein the siloxane-containing polymer has a Shore D hardness of at least 68.84.The material of any one of claims 1 to 82, wherein the siloxane-containing polymer has a Shore D hardness of at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75.85.The material of any one of claims 1 to 82, wherein the siloxane-containing polymer has a Shore D hardness of about 70-80.86.The material of any one of claims 1 to 85, wherein the siloxane-containing polymer does not contain fluorine.87.The material of any one of claims 1 to 87, wherein the one or more siloxane-containing monomers are non-cyclic monomers that do not contain a Si-containing cyclic ring.88.The material of any one of claims 1 to 87, wherein the ophthalmic device is a contact lens, an intraocular lens, or a corneal implant.89.The material of any one of claims 1 to 87, wherein the ophthalmic device is a contact lens.90.The material of claim 89, wherein the ophthalmic device is an extended wear lens.91.A siloxane-containing polymer , wherein the polymer is a polymerization product of a monomer mixture comprising:one or more high Tg cross linkers;one or more high Tg monomers; andone or more siloxane-containing monomers;wherein the siloxane-containing polymer has a Dk number of at least 45.92.The siloxane-containing polymer of claim 91, wherein the siloxane-containing polymer comprises a percolation structure that exceeds a percolation threshold.93.The siloxane-containing polymer of claim 65 or 66, wherein the siloxane-containing polymer is substantially free of PFAS material.94.A siloxane-containing polymer, wherein the polymer is a polymerization product of a monomer mixture comprising:one or more high Tg cross linkers;one or more high Tg monomers; andone or more siloxane-containing monomers;wherein the siloxane-containing polymer comprises a percolation structure.95.The siloxane-containing polymer of claim 94, wherein the siloxane-containing polymer is substantially free of PFAS material.96.The siloxane-containing polymer of any one of claims 92 to 95, wherein the percolation structure are percolated channels.97.The siloxane-containing polymer of claim 96, wherein the percolated channels are formed upon microphase separation of the siloxane-containing polymer.98.The siloxane-containing polymer of any one of claims 92 to 95, wherein the percolation threshold is sufficient to allow the permeation of oxygen.99.The siloxane-containing polymer of any one of claims 91 to 98, wherein the one or more siloxane-containing monomers comprise one or more bulky siloxane monomers.100.The siloxane-containing polymer of claim 99, wherein the one or more bulky siloxane monomers comprise Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane, or a combination thereof.101.The siloxane-containing polymer of any one of claims 91 to 100, wherein the one or more siloxane-containing monomers comprise one or more linear siloxane monomers.102.The siloxane-containing polymer of claim 101, wherein the one or more linear siloxane monomers comprise monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, or a combination thereof.103.The siloxane-containing polymer of any one of claims 91 to 98, wherein the one or more siloxane-containing monomers comprise Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propyl, bis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane, monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, or a combination thereof.104.The siloxane-containing polymer of any one of claims 91 to 98, wherein the one or more siloxane-containing monomers comprisea) a monomer of Formula (I) (I),whereinR1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;Y is -O-, -S- or -NH-;X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,n is an integer number selected from 0 to 100; andm is an integer number selected from 0 to 100,b) a monomer of Formula (II) (II),wherein n is an integer number selected from 0 to 100,orc) a monomer of Formula (III), (III),wherein:R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl;Y is -O-, -S- or -NH-;X is -O-, -S- , -NH-C=O-O- or -NH-C=O=NH- or -NH- ;n is an integer number selected from 0 to 100;I is an integer number selected from 0 to 100; andm is an integer number selected from 0 to 100,or a combination thereof.105.The siloxane-containing polymer of any one of claims 91 to 98, wherein the one or more siloxane-containing monomers comprisea) a monomer of Formula (I*), (I*),wherein:R1is hydrogen or C1-C3alkyl;each R2is independently C1-C4alkyl;Y is -O-, -S- or -NH-;X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-,n is an integer number selected from 0 to 100; andm is an integer number selected from 0 to 100,b) a monomer of Formula (II*) (II*),wherein:n is an integer number selected from 0 to 100; andeach R3is independently C1-C4alkyl,orc) a monomer of Formula (III*) (III*),wherein:R1is hydrogen or C1-C3alkyl;Y is -O-, -S- or -NH-;X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH- ;each R4is independently C1-C4alkyl;n is an integer number selected from 0 to 100;I is an integer number selected from 0 to 100; andm is an integer number selected from 0 to 100,or a combination thereof.106.The siloxane-containing polymer of any one of claims 91 to 98, wherein the one or more siloxane-containing monomers comprise one or more monomers from Tables 1 and 2.107.The siloxane-containing polymer of any one of claims 91 to 98, wherein the one or more siloxane-containing monomers comprise TRISMA, TRISNMA, TRISUREMA or any combination thereof.108.The siloxane-containing polymer of any one of claims 91 to 107, wherein the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 5 wt% to about 98 wt% of the monomer mixture.109.The siloxane-containing polymer of any one of claims 91 to 107, wherein the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 30 wt% to about 95 wt% of the monomer mixture.110.The siloxane-containing polymer of any one of claims 91 to 107, wherein the one or more siloxane-containing monomers are present in the monomer mixture in an amount of about 50 wt% to about 90 wt% of the monomer mixture.111.The siloxane-containing polymer of any one of claims 91 to 110, wherein the monomer mixture further comprises one or more siloxane-containing cross linkers.112.The siloxane-containing polymer of claim 111, wherein the siloxane-containing cross linkers comprises one or more methacrylate- / acrylate-terminated polydimethylsiloxanes, or methacrylamide polydimethylsiloxane, or a combination thereof.113.The siloxane-containing polymer of claim 111 or 112, wherein the siloxane-containing cross linkers comprises Methacryloxypropyl-Terminated Polydimethylsiloxane, Methacryloxypropyl-Terminated Branched Polydimethylsiloxane, (3-Acryloxy-2-hydroxypropoxypropyl) Terminated PolyDimethylsiloxane, methacrylamido propyl poly dimethylsiloxane, or a combination thereof.114.The siloxane-containing polymer of claim 111 or 112, wherein the siloxane-containing cross linkers comprises Methacylated poydimethylsiloxane.115.The siloxane-containing polymer of any one of claims 111 to 114, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 0.01 wt% to about 50 wt% of the monomer mixture.116.The siloxane-containing polymer of any one of claims 111 to 114, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 1 wt% to about 10 wt% of the monomer mixture.117.The siloxane-containing polymer of any one of claims 111 to 114, wherein the one or more siloxane-containing cross linkers are present in the monomer mixture in an amount of about 3 wt% to about 8 wt% of the monomer mixture.118.The siloxane-containing polymer of any one of claims 91 to 117, wherein the one or more high Tg cross linkers have a Tg of at least 80oC.119.The siloxane-containing polymer of any one of claims 91 to 117, wherein the one or more high Tg cross linkers have a Tg of at least 100oC.120.The siloxane-containing polymer of any one of claims 91 to 117, wherein the one or more high Tg cross linkers have a Tg of at least 110oC.121.The siloxane-containing polymer of any one of claims 91 to 120, wherein the one or more high Tg cross linkers comprise alkyl glycol dimethacrylate such as neopentyl glycol dimethacrylate.122.The siloxane-containing polymer of any one of claims 91 to 121, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture.123.The siloxane-containing polymer of any one of claims 91 to 121, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least about 5 wt% of the monomer mixture.124.The siloxane-containing polymer of any one of claims 91 to 121, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, or at least 15 wt% of the monomer mixture.125.The siloxane-containing polymer of any one of claims 91 to 124, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture.126.The siloxane-containing polymer of any one of claims 91 to 124, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture.127.The siloxane-containing polymer of any one of claims 91 to 124, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of at most 25 wt%, at most 20 wt%, at most 18 wt%, at most 17 wt%, at most 16 wt%, at most 15 wt%, at most 14 wt%, at most 13 wt%, at most 12 wt%, at most 11 wt%, at most 10 wt% of the monomer mixture.128.The siloxane-containing polymer of any one of claims 91 to 121, wherein the one or more high Tg cross linkers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture.129.The siloxane-containing polymer of any one of claims 91 to 128, wherein the one or more high Tg monomers have a Tg of at least 80oC.130.The siloxane-containing polymer of any one of claims 91 to 128,wherein the one or more high Tg monomers have a Tg of at least 100oC.131.The siloxane-containing polymer of any one of claims 91 to 128,wherein the one or more high Tg monomers have a Tg of at least 110oC.132.The siloxane-containing polymer of any one of claims 91 to 131, wherein the one or more high Tg monomers comprise alkyl substituted styrene monomer, adamantyl derivative, Isobronyl derivative, methacrylate, methacrylamide, or a mixture thereof.133.The siloxane-containing polymer of any one of claims 91 to 131, wherein the one or more high Tg monomers comprise methacrylic acid, mono, bi, tri methyl styrene, adamantyl methacrylate, isobornyl methacrylate, or a mixture thereof.134.The siloxane-containing polymer of any one of claims 91 to 131, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at least about 1 wt% of the monomer mixture.135.The siloxane-containing polymer of any one of claims 91 to 131, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at least about 10 wt% of the monomer mixture.136.The siloxane-containing polymer of any one of claims 91 to 131, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at least 5 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, or at least 50 wt% of the monomer mixture.137.The siloxane-containing polymer of any one of claims 91 to 136, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at most about 25 wt% of the monomer mixture.138.The siloxane-containing polymer of any one of claims 91 to 136, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at most about 15 wt% of the monomer mixture.139.The siloxane-containing polymer of any one of claims 91 to 136, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 12 wt%, at most 10 wt%, or at most 5 wt% of the monomer mixture.140.The siloxane-containing polymer of any one of claims 91 to 131, wherein the one or more high Tg monomers are present in the monomer mixture in an amount of about 5 wt% to about 15 wt% of the monomer mixture.141.The siloxane-containing polymer of any one of claims 91 to 140, wherein the monomer mixture further comprises one or more UV blocking agents, one or more blue blocker agents, or a combination thereof.142.The siloxane-containing polymer of claim 141, wherein one or more UV blocking agents and one or more blue blocker agents are present in the monomer mixture in an amount of 0 to 1 wt% of the monomer mixture.143.The siloxane-containing polymer of claim 141, wherein one or more UV blocking agents and one or more blue blocker agents are present in the monomer mixture in an amount of 0 to 0.1 wt% of the monomer mixture.144.The siloxane-containing polymer of any one of claims 91 to 143, wherein the siloxane-containing polymer has a Dk number of at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, or at least 200.145.The siloxane-containing polymer of any one of claims 91to 144, wherein the siloxane-containing polymer has a Shore D hardness of at least 70 (e.g., 70-80).146.The siloxane-containing polymer of any one of claims 91 to 144, wherein the siloxane-containing polymer has a Shore D hardness of at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75.147.The siloxane-containing polymer of any one of claims 91 to 144, wherein the siloxane-containing polymer has a Shore D hardness of about 70-80.148.The siloxane-containing polymer of any one of claims 91 to 147, wherein the siloxane-containing polymer does not contain fluorine.149.The siloxane-containing polymer of any one of claims 91 to 148, wherein the polymer is manufactured by in situ.150.The siloxane-containing polymer of any one of claims 91 to 148, wherein the polymer is manufactured by a solvent-free process.151.A material comprising the siloxane-containing polymer of any one of claims 91 to 148152.The material of claim 151, further comprising one or more additives (e.g.., dyes, UV blockers, blue blocker reagent).153.A method of making a siloxane-containing polymer of any one of claims 91 to 148, or a material of claim 151-152, wherein the method comprises polymerizing the monomer mixture.154.The method of claim 153, wherein the method comprises curing such as thermal curing or photo curing.155.The method of claim 153 or 154, wherein the method comprises solvent-free polymerization.156.The method of any one of claims 153 to 155, wherein the method comprises molding (e.g,. molding using casting and injection).157.The method of any one of claims 153 to 155, wherein the method comprises molding in a mold.158.The method of claim 157, wherein the mold is a thermoplastic, thermosets, or silicon rubber.159.The method of claim 157, wherein the mold is has a rod shape.160.The method of claim 157, wherein the mold is has a button shape.161.The method of claim 159 or 160, wherein the mold has a base curvature (e.g., flat and curved).162.A method of producing high Tg, rigid, tough, fluorine-free and PFAS-free materials with medium to ultrahigh Dk numbers which comprises some or all:a) One or more bulky siloxane materials with reactive moieties such as methacrylate, methacrylamide, with or without urethan or urea linkage;b) One or more linear siloxane reactive materials with mono or multi reactive moieties;c) One or more an alkyl glycol dimethacrylate;c) One or more high Tg hydrophilic monomers ;d) One or more high Tg hydrophobic monomers such as cyclic monomers (adamantyl methacrylate or Isobornyl methacrylate but not limited to) and styryl monomers such as alkyl styrene (2,4,6) tri methyl styrene;e) UV blocking agents and blue blocker agents;the reaction being conducted within positive pressure of inert gas from few pascal to several mega pascal using thermal or photopolymerization under temperature from 25 C to 150 C or uv to low energy lights.163.The method of claim 162, wherein the bulky siloxane is Methacryloxypropyltris(trimethylsiloxy)silane, (3-Methacrylamidopropyl) bis(trimethylsiloxy)methylsilane, 3-(3-Methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, Methacryloxypropylbis(trimethylsiloxy)silanol, Acrylamidopropyltris(trimethylsiloxy)silane or mixture of them however not limited to; the linear polysiloxane is asymmetric of silicon monomers such as monoMethacryloxypropyl terminated PDMS, monoMethacryloxypropyl branched PDMS, methacrylamido propyl poly dimethylsiloxane; the methacryl functional terminated polydimethylsiloxane is 4-methacryloxybutyl terminated polydimethylsiloxane but not limited to, and poly siloxane cross linker is metacrylate or methacryl amide polydimethyl siloxane and medium to high Tg cross linker is alkyl glycol dimethacrylate such as neopentyl glycol dimethacrylate; high Tg hydrophobic monomers such as alkyl substituted styrene monomers, adamantyl derivative and Isobronyl derivitives methacrylate or methacrylamide; the hydrophilic agent is methacrylic acid.164.The method of claim 163, wherein the reactive siloxane derivatives comprises 10% to 85 wt% of the material, by weight.165.The method of claim 162, wherein the hydrophilic reactive monomers comprises between 0% to 20% of the material, by weight.166.The method of claim 162, wherein the reactive hydrophobic monomers comprises 10 to 40 wt% of the material.167.The method of claim 162, wherein the cross linkers comprises 1 to 20 wt% of the material.168.The method of claim 162, wherein the reactive UV or blue light blockers (un reactive or reactive) comprises 0 to 1 wt% of the material.169.The method of claim 162, wherein the reactive or unreactive dyes in different colors comprises 0 to 0.1 wt% of the material.170.The method of claim 162, wherein the reaction is conducted under inert gas such as nitrogen, argon or helium atmosphere, purging for some minutes and under pressure from a few mbar to 100 bars.171.The method of claim 162 wherein the reaction is conducted using thermal initiator or photo initiator.172.The method of claim 168, wherein the reaction is conducted at room temperature to 150oC with temperature profile.173.The method of claim 168, wherein the reaction is conducted under light using wavelength from UV to visible light.174.The method of claim 163, wherein the reaction is conducted within a mold that the mold can be any shape such as button, rod, button with one base curvature or two base curvatures or in a mold with a final shape of a lens.175.The method of claim 163, wherein mold is selected whereby the hyper Dk material is injected or printed as a button with flat base surface, a button with curvature one or both base surfaces, a lens, or a rod using injection molding or 3D printer.176.The method of claim 163, wherein the mold (one or more than one mold) can placed in a vessel with any shape that can be purged or pressurized with inert gas and heated or irradiated by light.HYPER GAS PERMEABLE MATERIALS FOR OPHTHALMIC APPLICATIONS

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