Transparent polymeric material free of elemental fluorine with high oxygen diffusion

Abstract

The invention discloses a fluorine-free transparent polymer material with high oxygen permeability. The fluorine-free transparent polymeric material comprises at least one silicone cage compound having at least one polymerizable hanging group and up to seven side chains, at least one acrylic compound, at least one acrylate-functionalized compound, and a styryl tris (trimethylsiloxy) silane. Any compound of the transparent polymeric material does not contain elemental fluorine. The first polyhedral oligomeric silsesquioxane (POSS) monomeric silicone cage has one polymerizable methacrylate suspending group and seven isoalkyl side chains, and the second polyhedral oligomeric silsesquioxane (POSS) monomeric silicone cage has two polymerizable methacrylate suspending groups and six isoalkyl side chains. The transparent polymeric material has a Dk of about 150 and a Shore D hardness greater than 70.

Description

Technical Field

[0001] This invention relates to fluorine-free, highly permeable (Dk) materials and methods thereof; and more specifically, to high Dk materials having a Dk value greater than 100; and even more specifically, to high Dk materials suitable for use as rigid gas-permeable contact lenses (including rigid gas-permeable lenses). Background Technology

[0002] Contact lens materials are transparent materials made from highly cross-linked organic polymers. Two types of lenses are available: soft and hard. Soft lenses are classified as silicone hydrogels, which are composed of soft silicone polymers combined with hydrophilic polar materials. This combination of properties makes silicone hydrogels a preferred choice for patient eye comfort. Unfortunately, silicone hydrogel lenses have low oxygen permeability, which may cause eye damage over time.

[0003] On the other hand, rigid gas permeable (RGP) lenses are typically hydrophobic and may require surface modification to achieve good wetting in the eye. Wetting in RGP lenses is achieved by adding acids that rearrange the lens surface. As the name suggests, RGP lenses have increased oxygen permeability. This property of allowing oxygen to be transported through the material is an important advantage for eye health. Unfortunately, RGP lenses contain fluorinated acrylates, which can be harmful to the environment and pose a hazard to wearers who come into contact with the lenses.

[0004] Incorporating fluorinated acrylates into lenses increases their mechanical properties by making them harder. At the same time, these materials have higher oxygen permeability than materials without these monomers. One of the most useful monomers is hexafluoroisopropyl methacrylate (HFiPMA).

[0005]

[0006] However, due to health concerns, fluorinated compounds have recently become a target for removal from many products. Numerous studies on polyfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) have found high levels of fluorinated materials in the blood of the general public. PFOA is a common precursor used to prepare perfluorooctane sulfonic acid (PFOS), which contains acrylate monomers.

[0007] Recent attempts to remove fluoride monomers from contact lenses have not been successful. To date, substitution of fluoride compounds in RGP lenses has demonstrated significant property degradation. For example, replacing HFiPMA with methyl methacrylate (MMA) results in an 87% decrease in oxygen permeability; replacing HFiPMA with 3-methacryloyloxypropyltris(trimethylsiloxy)silane (TRIS) produces a material that is difficult to machine; and a 1 / 1 mixture of MMA and TRIS replacing HFiPMA reduces oxygen permeability by about half and significantly reduces the hardness, flexural modulus, and wettability of the resulting material.

[0008] Polyhedral oligomeric silsesquioxane (POSS) monomers have been incorporated into ophthalmic materials. In one instance, U.S. Patent 6,586,548 ('548 Patent) teaches the polymerization of vinyl monomers for biocompatible materials, wherein one component is a POSS monomer. POSS monomers can have a single olefinically unsaturated group as a polymerizable functional group. These materials can be transparent and suitable for contact lenses; however, these materials have low oxygen permeability, with Dk values ​​ranging from approximately 17 to 34.

[0009] In another example, U.S. Patent 7,198,639 ('639 Patent) uses hydrosilylation, which involves reacting hydrides with vinyl groups and a platinum catalyst, to incorporate POSS cages into soft lenses. Alternatively, free radical polymerization is used to incorporate acrylic and / or styrene groups into the POSS cages. POSS molecules functionalized with alcohol, amine, thiol, epoxy, and isocyanate groups have also proven useful in the '639 Patent. POSS molecules are multifunctional, with three functional groups originating from the apex of the open cage. These polymer compositions can be used to create intraocular lens (IOL) implants, corneal inlays, and other related objects. However, since these materials are intended for implantation in the eye, their oxygen transport properties have not been reported.

[0010] In yet another example, U.S. Patent 10,633,472 ('472 patent) describes a method for preparing materials with high oxygen transport (high Dk). Monomers include fluorinated acrylates, hydroxyalkyltris(trimethylsiloxy)silanes, hydroxyalkyl-terminated polydimethylsiloxanes, and styrylethyltris(trimethylsiloxy)silanes (styryltrisilanes). Crosslinking agents such as alkyl glycol dimethacrylates and hydrophilic agents such as methacrylic acid are also included, wherein the Dk value is greater than 175. These materials can also be lathe-machined into rigid gas permeable (RGP) contact lenses.

[0011] In a further example, POSS methacrylate is incorporated into poly(urethane), as disclosed in publication number WO2016 / 115507. The cured polymer compositions are suitable for intraocular lenses and contact lenses, while urethane-based acrylate copolymers are also suitable for other corneal prostheses.

[0012] In a final example, U.S. Patent Application 2022 / 0380599 describes a high-Dk contact lens material containing a POSS cage having at least two polymerizable groups and at least two hydrophilic groups. However, it should be noted that fluorinated acrylates are incorporated into these materials. Summary of the Invention

[0013] According to one aspect of the invention, a novel class of ophthalmic devices primarily made of organosilicon is formed as transparent materials possessing high oxygen permeability (Dk > 100). These organosilicon materials are shaped to exhibit high Dk RGP lenses in the absence of fluorinated comonomers. The organosilicon monomers used in place of fluorinated monomers are polyhedral oligomeric silsesquioxane (POSS) cages having at least one polymerizable group and multiple organic functional groups. Furthermore, POSS monomers having two sites available for polymerization allow the silsesquioxane cages to be incorporated into the main chain of a macromolecule. In this way, the architecture of the resulting polymer differs for POSS monomers having a single polymerizable group, wherein the resulting organosilicon cage is suspended on the polymer main chain.

[0014] Furthermore, POSS monomers with more than two polymerizable groups form a gel-like structure. By incorporating POSS cages into the polymer backbone, the resulting polymer can have a structure with interconnected organosilicon cages arranged in a linear array, or it can be combined with other polymerizable monomers to form a linear copolymer. The POSS cages suspended on the polymer chain can be generated by the polymerization of POSS molecules with one or more polymerizable groups.

[0015] Typically, fluorinated monomers are combined with silicones to obtain high-dk materials with properties suitable for lens formation. However, combining POSS silicones with other silicones produces materials that are transparent and have good mechanical properties. Organofunctional silicones can include acrylates, methacrylates, styrene derivatives, and itaconic acid esters as polymerizable groups. Attached Figure Description

[0016] The subject matter will now be described in detail with reference to the accompanying drawings, which are provided as illustrative examples to enable those skilled in the art to practice the subject matter. It should be noted that the drawings and examples are not intended to limit the scope of the subject matter to a single embodiment, but rather other embodiments are possible by interchange of some or all of the elements described or shown, and further wherein:

[0017] Figure 1 This is a table showing exemplary compositions for forming non-fluorinated polymer materials according to the invention, wherein a thermal initiator is used in the polymerization reaction;

[0018] Figure 2 It shows the use Figure 1 A table of characterization data for exemplary non-fluorinated polymer materials produced by the exemplary compositions listed below;

[0019] Figure 3 This shows the calculations used for such... Figure 1 The graph shows the reciprocal transmittance of the Dk value versus thickness for Comparative Example 1 listed in the document.

[0020] Figure 4 This shows the calculations used for such... Figure 1 The graph shows the reciprocal of the Dk value versus the thickness for Example 1 listed in the document; and

[0021] Figure 5 This shows the calculations used for such... Figure 1 The graph of the reciprocal transmittance of the Dk value versus thickness for Example 3 listed in the document.

[0022] Figure 6 This is a table showing exemplary compositions for forming non-fluorinated polymer materials according to the invention, wherein a photoinitiator is used in the polymerization reaction;

[0023] Figure 7 It shows the use Figure 6 A table of characterization data for exemplary non-fluorinated polymer materials produced by the exemplary compositions listed herein; and

[0024] Figure 8 This is to show the measurement used. Figure 6 The exemplary compositions listed herein produce exemplary non-fluorinated polymer materials with glass transition temperatures of bifunctional POSS as tan(δ) versus weight percentage. Detailed Implementation

[0025] Rigid, breathable monolithic material is cut into the shape of the lens to improve vision for patients with astigmatism. Early lenses were made of poly(methyl methacrylate). Through many generations of fluorinated acrylates and silicones, oxygen permeability and wettability have been improved. This has increased both patient comfort and intraocular health.

[0026] As described below, one aspect of the present invention relates to biocompatible materials, such as POSS cages, that replace fluorinated components with siloxanes. POSS cages have a relatively high molecular weight and have at least one, and typically two or more, polymerizable groups attached to the silsesquioxane cage. POSS cages can be more accurately described as macromonomers rather than monomers. As described in more detail below, by skillfully selecting the POSS macromonomer, transparent materials with properties suitable for contact lenses with high oxygen permeability can be produced. Unlike the materials described herein, previous high-Dk contact lens formulations included a high proportion of fluorinated segments.

[0027] The siloxanes used in contact lens synthesis are typically linear and branched siloxanes. Linear siloxanes include organosilicon polymers such as polydimethylsiloxane, which generally conform to the molecular formula R2SiO, where two methyl groups are bonded to silicon atoms and each silicon atom has a bridging oxygen group. They are usually functionalized at one or both ends with polymerizable groups. The small molecule pentamethyldisiloxane methyl methacrylate (structure (I)) is a simple form of linear siloxane.

[0028]

[0029] The TRIS group is a branched siloxane in which a central silicon atom is bonded to an organic group that may also contain polymerizable groups. The three groups bonded to the central silicon atom consist of silicon-oxygen bonds bonded to the other silicon atoms. The central atom of the TRIS structure has the formula RSiO. l.5 Gaylord's early description of the TRIS-type molecule in U.S. Patent 3,808,178 was structure (II), namely 3-[tris(trimethylsiloxy)silyl]propyl methacrylate.

[0030]

[0031] The third type of organosilicon that can be used in contact lenses is a silicon-cage molecule based on an oxygen and silicon tetrahedral structure. Silicon atoms are essentially bonded to other silicon atoms via siloxane bonds, and one of the simplest structures formed by this arrangement is cubic, as generally shown in structure (III). These silsesquioxane molecules also conform to the formula RSiO. 1.5Unlike TRIS molecules, these form 3D structures. These molecules are named POSS, representing polyhedral oligomeric silsesquioxanes. POSS molecules can have a silica-like core and organic side groups covalently attached to the vertices of an inorganic polyhedron, and are generally considered to bridge the gap between organic and inorganic materials. Through clever chemical selection, properties representing the optimal state of each component can be obtained. Structure (III) is an idealized POSS cage with two polymerizable groups, and the remaining vertices contain isobutyl co-substituents. POSS III is commercially available from Hybrid Plastics (Hattiesburg, Mississippi) under product number HC0709.13.

[0032]

[0033] Highly functionalized POSS cages can be linked together via acrylate side groups during polymerization. Due to their combination of high molecular weight (typically greater than 1000 amu) and high functionality, the cages are essentially prepolymers or macromonomers. The functionality is locked in place during polymerization and extends throughout the material, and phase separation is minimized. This results in the extension of isobutyl side groups throughout the polymer matrix.

[0034] A POSS cage is part of a polymer backbone in which polymer chains extend from each side of the cage. These POSS molecules can be classified as distal chelate monomers that polymerize with themselves or with other monomers to incorporate the POSS cage into the polymer backbone. These can then be considered distal chelate oligomers. The distal chelate monomer / oligomer / polymer is a bifunctional polymer in which both ends have the same functionality. In this way, flexible polymerizable groups can be used to incorporate cage-like silicones into the polymer backbone to produce flexible and durable materials. According to one aspect of the invention, a POSS cage having two polymerizable groups allows for the design of contact lens materials that can be either soft or rigid and simultaneously exhibit high oxygen transport.

[0035] POSS cages with a single polymerizable group are also useful. By way of example, a POSS cage incorporating a propyl methacrylate polymerizable group can be incorporated into a polymer network as a suspended POSS cage. The remaining side groups can be a large number of organic parts. By way of example, but not limited to, the isobutyl side groups form a crystalline product, which is commercially available as a white powder from Hybrid Plastics (Hattiesburg, Mississippi) under product number MA0702. The crystallinity of the isobutyl product indicates that the molecule is a single-cage structure typically represented by POSS structure IV. In a further example, the incorporation of isooctyl side groups forms an amorphous POSS molecule with the general structure shown as POSS V, which is commercially available as a transparent liquid from Hybrid Plastics (Hattiesburg, Mississippi) under product number MA0719. In contrast to POSS IV, the isooctyl-derived cages of POSS V can be a mixture of cages of different sizes. That is, POSS V can be a mixture of silsesquioxane cages containing 8, 10, or 12 silicon atoms. It should also be noted that each POSS molecule in a POSS molecule can be a mixture of silsesquioxane cages, wherein functionality (e.g., methacrylate side groups) is randomly distributed around the cages. Therefore, the accompanying figures do not represent precise structures, but rather rather rather idealized structures.

[0036]

[0037] R = Isobutyl:POSS (IV)

[0038] Isooctyl: POSS (V)

[0039] Isobutyl: POSS (VI) amorphous

[0040] Unlike POSS (IV), which is a crystalline compound with a precise cage size of 8 silicon atoms, amorphous POSS (VI) is a mixture of both larger open and closed cages. POSS (VI) is more compatible with other monomers in formulations. It is more soluble in organic solvents than crystalline POSS (IV).

[0041] According to a further aspect of the invention, a method for producing a high-Dk material (Dk greater than 100) comprises contacting and reacting the following substances: one or more POSS methacrylates; alkyl glycol dimethacrylates; hydrophilic agents, such as methacrylic acid; methacrylamide-functionalized tris(trimethylsiloxy)silanes; methacrylamide-functionalized end-capped polydimethylsiloxanes; and styryltris(trimethylsiloxy)silanes. By way of example, but not limited thereto, the POSS may be a combination of isobutyl POSS of structure (III) HC0709.13 and structure (IV) MA0702, the alkyl glycol dimethacrylate may be neopentyl glycol dimethacrylates; the methacrylamide-functionalized tris(trimethylsiloxy)silane may be 3-methacryloyloxypropyltris(trimethylsiloxy)silane; and the methacrylamide-functionalized end-capped polydimethylsiloxane may be 4-methacryloyloxybutyl-terminated polydimethylsiloxane. Further exemplary compositions may also contain added 1,3-bis(3-(methacryloyloxy)propyl)1,1,3,3-tetra(trimethylsiloxy)disiloxane (tridimer).

[0042] The reaction can be carried out for a period of time in an inert atmosphere (e.g., under nitrogen, argon, and / or helium) and at a temperature sufficient to produce a high-Dk material. The reaction can be carried out at room temperature, for example, between about 20°C and about 25°C when a photoinitiator is present, or at elevated temperatures such as up to about 100°C when a thermal initiator is added to the formulation. Therefore, the high-Dk material can have a Dk value greater than 100. On the other hand, if a hydrophilic agent such as methacrylic acid is incorporated into the polymer matrix, the high-Dk material prepared according to the invention does not require surface treatments such as plasma treatment. Additionally, as used herein, the terms “about” and “approximately” should be interpreted as within plus or minus five percent (+ / - 5%) of the stated value when associated with any value.

[0043] advantage

[0044] Exemplary non-limiting advantages of the present invention may include:

[0045] a) Fluorine is not present in the polymer matrix;

[0046] b) The material is mainly composed of several different forms of siloxanes;

[0047] c) The material is transparent;

[0048] d) The dried material is hard enough to be formed into an ophthalmic lens on a lathe;

[0049] e) The material can be polymerized in a mold and directly formed into lenses or buttons;

[0050] f) The level of crosslinking can be controlled by mixing a POSS cage with a single polymerizable group with a POSS cage with two or more polymerizable groups; and

[0051] g) Due to the high molecular weight of the POSS macromonomer, less shrinkage occurs during polymerization.

[0052] Example

[0053] The following examples are for demonstration purposes only and do not imply that this disclosure is limited thereto.

[0054] I. Thermally polymerized rods

[0055] Non-fluorinated RGP samples containing 40% POSS (which replaces HFIPMA) were prepared as described below. In three cases, the polymer rods containing POSS were formed into discs or buttons. The buttons are light-transmitting and possess good mechanical properties suitable for lathe machining into lenses. The compositions of each example are shown below. Figure 1 Table 1 shows the oxygen permeability measured using a Dk polarographic cell, and reported along with hardness and appearance. Figure 2 As shown in Table 2. It should also be noted that, alternatively, buttons or lenses can be made directly from polypropylene molds using ultraviolet or blue light.

[0056] Examples 1 to 3, as shown in Table 1, were prepared by thermal polymerization using the peroxide initiator LUPEROX P. Each of Examples 1 to 3 consisted of 90% by weight or more of siloxane monomers and was free of fluorine components. The polymerization reaction was carried out at 55°C and 95°C under nitrogen. Each temperature was held for 24 hours and reached with a 6-hour ramp-up time. The polymerized rods were removed from the shell and annealed at 120°C for 24 hours. Residual monomers and oligomers were extracted by soaking in dichloromethane (DCM) overnight. The extraction level was low, and the shape of the buttons was not affected by the solvent. It should be noted that the relative weight percentages of the components in the compositions do not include any mass or associated weight percentage added by the initiator.

[0057] like Figure 2 The tan δ peaks shown in Table 2 were obtained through dynamic mechanical analysis (DMA) and indicate that the glass transition temperature (Tg) of the button is between 140°C and 155°C. The Shore D hardnesses of Examples 1 and 2 are 70 and 72, respectively. The Dk values ​​for each example are determined by... Figures 3 to 5 The slope of the line in the diagram is determined by the reciprocal of its slope. Note that Comparative Example 1 does not contain any POSS material; instead, it is made of fluorinated acrylate. Figure 2 As shown, the characteristics of the example are similar to those of the comparative example, but it is worth noting that it does not contain fluorinated acrylates or any other fluorinated materials.

[0058] II. Photopolymerization forms buttons.

[0059] Polymer buttons were produced by photopolymerization in a nitrogen chamber at room temperature. Polypropylene molds were used to produce buttons with a diameter of approximately 15 mm and a thickness of approximately 5 mm. A Dymax 400W floodlight curing system with a peak wavelength of 370 nm was used, and the polymerization time was approximately 10 minutes. The composition is compiled as follows: Figure 6 Table 3 in the table. (For example...) Figure 6 As shown, Examples 4 to 13 are all fluorine-free. Similar to the thermal polymerization described above, the POSS cage provides a fully silicone network while also offering good mechanical properties. Therefore, the POSS macromonomer provides all the advantages of fluorinated acrylates without introducing the PFAS moiety. It should also be noted that Comparative Examples 2 and 3 used the same method as Comparative Example 1 (… Figure 1 The same fluorinated composition.

[0060] like Figure 6 As shown in Table 3, Examples 4, 6, 8, and 10 have the same composition as Examples 5, 7, 9, and 11, respectively, except that the even-numbered groups use the UV initiator 2-hydroxy-2-methylphenylacetone, while the odd-numbered groups use the blue light initiator diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO). Various combinations of POSS III and POSS IV were used in the experiments (Table 3). Notably, POSS V from Examples 4 to 11 was photopolymerized with HMPP in Example 12 and with TPO in Example 13.

[0061] All the buttons were transparent and underwent minimal extraction after soaking in DCM overnight. The mechanical properties of Examples 4 through 13 are summarized in... Figure 7 Table 4 shows the properties consistent with those used to make contact lenses. Examples 12 and 13 demonstrate that amorphous POSS molecules (POSS V) having a polymerizable group can be polymerized into transparent polymer materials with mechanical properties consistent with those of gas-permeable lenses. Notably, Examples 4 to 11 (POSS IV) also formed transparent materials with mechanical properties consistent with those of gas-permeable lenses.

[0062] The maximum value of the Tan (δ) peak is the glass transition temperature measured by DMA, such as Figure 8 The drawings show instances 4, 6, and 8 represented by squares, and instances 5, 7, and 9 represented by circles. (See diagram below.) Figure 8 As can be seen, Tg increases with increasing crosslinking agent content, as reflected by the increased level of bifunctional POSS III (HC0709.13), resulting in a higher Tg.

[0063] As can be seen from the above description with reference to the accompanying figures, the properties of materials prepared with POSS compounds are similar to those of materials prepared with fluorinated monomers. Therefore, compared with the prior art, contact lens materials can be manufactured without the use of fluorine.

[0064] The detailed description set forth herein in conjunction with the accompanying drawings is intended as a description of exemplary embodiments in which the subject matter currently disclosed may be practiced. The term "exemplary" as used throughout this specification means "serving as an example, instance, or illustration" and should not necessarily be construed as preferred or advantageous over other embodiments.

[0065] The foregoing description of the embodiments is intended to enable any person skilled in the art to make and use the subject matter. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the novel principles and subject matter disclosed herein may be applied to other embodiments without employing inventiveness. The claimed subject matter set forth in the claims is not intended to be limited to the embodiments shown herein, but is accorded the widest scope consistent with the principles and novel features disclosed herein. Additional embodiments are contemplated within the spirit and true scope of the disclosed subject matter. Claims (as amended under Article 19 of the Treaty) 1. A fluorine-free transparent polymer material with high oxygen permeability, said fluorine-free transparent polymer material comprising: a) at least one organosilicon cage-like compound having at least one polymerizable suspended group and at most seven side chains; b) At least one acrylic acid compound; c) At least one acrylate-functionalized compound; d) Styrene tris(trimethylsiloxy)silane; wherein, None of the compounds constituting the transparent polymer material contain elemental fluorine; and, The at least one organosilicon cage is a first polyhedral oligomeric silsesquioxane (POSS) monomer having a polymerizable methacrylate suspending group and seven isoalkyl side chains. 2. The fluorine-free transparent polymer material according to claim 1, wherein the fluorine-free transparent polymer material further has a Dk of approximately 150 and a Shore D hardness greater than 70. 3. The fluorine-free transparent polymer material according to claim 1, wherein the fluorine-free transparent polymer material further has a Dk of approximately 125 and a Shore D hardness greater than 70. 4. The fluorine-free transparent polymer material according to claim 1, wherein at least one silicone cage accounts for at least 40% by weight of the polymer material. 5. The fluorine-free transparent polymer material according to claim 1, wherein the at least one organosilicon cage is a second POSS monomer having two polymerizable methacrylate suspending groups and six isoalkyl side chains. 6. The fluorine-free transparent polymer material according to claim 5, wherein the isoalkyl side chains of the first POSS monomer and the second POSS monomer are isobutyl side chains, isooctyl side chains, or both. 7. The fluorine-free transparent polymer material according to claim 5, wherein the isoalkyl side chains of the first POSS monomer and the second POSS monomer are both isobutyl side chains. 8. The fluorine-free transparent polymer material according to claim 1, wherein the fluorine-free transparent polymer material further comprises at least one disiloxane compound. 9. The fluorine-free transparent polymer material according to claim 8, wherein the at least one disiloxane compound is 1,3-bis(3-(methacryloyloxy)propyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane. 10. The fluorine-free transparent polymer material according to claim 1, wherein the at least one acrylic compound is methacrylic acid. 11. The fluorine-free transparent polymer material according to claim 1, wherein the at least one acrylate-functionalized compound is one or more of alkyl diol dimethacrylate, methacryl-functionalized tris(trimethylsiloxy)silane, and methacryl-functionalized end-capped polydimethylsiloxane. 12. The fluorine-free transparent polymer material according to claim 11, wherein the alkyl diol dimethacrylate is neopentyl glycol dimethacrylate. 13. The fluorine-free transparent polymer material according to claim 11, wherein the methacryloyl-functionalized tris(trimethylsiloxy)silane is 3-methacryloyloxypropyltris(trimethylsiloxy)silane. 14. The fluorine-free transparent polymer material according to claim 11, wherein the methacryloyl-functionalized end-capped polydimethylsiloxane is 4-methacryloyloxybutyl-terminated polydimethylsiloxane. 15. The fluorine-free transparent polymer material according to claim 11, wherein the at least one organosilicon cage, the styryltris(trimethylsiloxy)silane, the methacrylamide-functionalized tris(trimethylsiloxy)silane, and the methacrylamide-functionalized end-capped polydimethylsiloxane constitute at least 90% of the transparent polymer material. 16. The fluorine-free transparent polymer material according to claim 1, wherein the fluorine-free transparent polymer material further comprises a thermal polymerization initiator. 17. The fluorine-free transparent polymer material according to claim 1, wherein the fluorine-free transparent polymer material further comprises a UV polymerization initiator. 18. The fluorine-free transparent polymer material according to claim 1, wherein the fluorine-free transparent polymer material further comprises a blue light polymerization initiator.

Claims

1. A fluorine-free transparent polymeric material having high oxygen permeability, the fluorine-free transparent polymeric material comprising: a) at least one organosilica cage compound having at least one polymerizable pendant group and up to seven side chains; b) at least one acrylic compound; c) at least one acrylate functionalized compound; and, d) a styryl tris(trimethylsiloxy)silane, wherein all compounds making up the transparent polymeric material are free of elemental fluorine.

2. The fluorine-free transparent polymeric material of claim 1, wherein Dk is about 150 and Shore D hardness is greater than 70.

3. The fluorine-free transparent polymeric material of claim 1, wherein Dk is about 125 and Shore D hardness is greater than 70.

4. The fluorine-free transparent polymeric material of claim 1, wherein the at least one organosilica cage comprises at least 40 wt% of the polymeric material.

5. The fluorine-free transparent polymeric material of claim 1, wherein the at least one organosilica cage is a first polyhedral oligomeric silsesquioxane (POSS) monomer having one polymerizable methacrylate pendant group and seven isoalkyl side chains.

6. The fluorine-free transparent polymeric material of claim 5, wherein the at least one organosilica cage is a second POSS monomer having two polymerizable methacrylate pendant groups and six isoalkyl side chains.

7. The fluorine-free transparent polymeric material of claim 6, wherein the isoalkyl side chains of the first and second POSS monomers are iso-butyl side chains, iso-octyl side chains, or both.

8. The fluorine-free transparent polymeric material of claim 6, wherein the isoalkyl side chains of the first and second POSS monomers are both iso-butyl side chains.

9. The fluorine-free transparent polymeric material of claim 1, further comprising at least one disiloxane compound.

10. The fluorine-free transparent polymeric material of claim 9, wherein the at least one disiloxane compound is 1,3-bis(3-(methacryloyloxy)propyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane.

11. The fluorine-free transparent polymeric material of claim 1, wherein the at least one acrylic compound is methacrylic acid.

12. The fluorine-free transparent polymeric material of claim 1, wherein the at least one acrylate functionalized compound is one or more of an alkyl glycol dimethacrylate, a methacryloyl functional tris(trimethylsiloxy)silane, and a methacryloyl functional blocked polydimethylsiloxane.

13. The fluorine-free transparent polymeric material of claim 12, wherein the alkyl glycol dimethacrylate is neopentyl glycol dimethacrylate.

14. The fluorine-free transparent polymeric material of claim 12, wherein the methacryloyl functional tris(trimethylsiloxy)silane is 3-methacryloyloxypropyl tris(trimethylsiloxy)silane.

15. The fluorine-free transparent polymeric material of claim 12, wherein the methacryloyl-functional, endblocked polydimethylsiloxane is a 4-methacryloyloxybutyl endblocked polydimethylsiloxane.

16. The fluorine-free transparent polymeric material of claim 12, wherein the at least one organosilica cage, the styryl tri (trimethylsiloxy) silane, the methacryloyl-functional tri (trimethylsiloxy) silane, and the methacryloyl-functional, endblocked polydimethylsiloxane comprise at least 90% of the transparent polymeric material.

17. The fluorine-free transparent polymeric material of claim 1, further comprising a thermal polymerization initiator.

18. The fluorine-free transparent polymeric material of claim 1, further comprising a UV polymerization initiator.

19. The fluorine-free transparent polymeric material of claim 1, further comprising a blue light polymerization initiator.

Images