Multifunctional crosslinkers and ophthalmic devices formed therefrom - Patents.com

Abstract

The multifunctional crosslinker comprises one or more repeating units of a siloxanyl group or a silyl-alkyl-siloxanyl group and at least two ethylenically unsaturated reactive end groups, one of which is a (meth)acrylate-containing or acrylamide-containing reactive end group and the other of which is an allyl-containing or vinyl-containing reactive end group. The ophthalmic device is formed from the polymerization product of a monomer mixture containing one or more of the multifunctional crosslinkers, one or more first ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with the (meth)acrylate-containing or acrylamide-containing reactive end group of the multifunctional crosslinker, and one or more second ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with the allyl-containing or vinyl-containing reactive end group of the multifunctional crosslinker.

Description

[Technical field]

[0001] Claiming priority This application claims priority to U.S. Provisional Patent Application No. 63 / 305,728, entitled "Multifunctional Crosslinking Agents and Ophthalmic Devices Formed Therefrom," filed February 2, 2022, and incorporated herein by reference in its entirety. [Background technology]

[0002] Ophthalmic devices such as contact lenses are made from a variety of polymeric materials, including rigid gas-permeable materials, soft elastomeric materials, and soft hydrogel materials. The majority of contact lenses sold today are made from soft hydrogel materials. Hydrogels are crosslinked polymer systems that absorb and retain water, typically 10 to 80 percent by weight. Hydrogel lenses are generally prepared by polymerizing a lens-forming monomer mixture. In the case of silicone hydrogel lenses, silicone-containing monomers are copolymerized with hydrophilic monomers.

[0003] In the field of ophthalmic devices, various physical and chemical properties, such as oxygen permeability, wettability, material strength, and stability, are some of the factors that must be carefully balanced to provide a usable contact lens. For example, oxygen permeability is an important feature for certain contact lens materials, since the cornea receives its oxygen supply from contact with the atmosphere. Wettability is also important in that if the lens is not sufficiently wetted, it will not remain lubricated and therefore will not be comfortable to wear on the eye. Therefore, an optimal contact lens will have at least both excellent oxygen permeability and excellent tear wettability. Summary of the Invention

[0004] According to an exemplary embodiment, the multifunctional crosslinker comprises one or more repeat units of a siloxanyl group or a silyl-alkyl-siloxanyl group and at least two ethylenically unsaturated reactive end groups, one of which is a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group and the other of which is an allyl-containing reactive end group or a vinyl-containing reactive end group.

[0005] According to another exemplary embodiment, an ophthalmic device that is a polymerization product of a monomer mixture comprising:

[0006] (a) one or more multifunctional crosslinkers comprising one or more repeat units of a siloxanyl group or a silyl-alkyl-siloxanyl group and at least two ethylenically unsaturated reactive end groups, one of the at least two ethylenically unsaturated reactive end groups being a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group and the other of the at least two ethylenically unsaturated reactive end groups being an allyl-containing reactive end group or a vinyl-containing reactive end group;

[0007] (b) one or more first ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with a (meth)acrylate-containing or acrylamide-containing reactive end group of the multifunctional crosslinker;

[0008] (c) one or more second ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with the allyl- or vinyl-containing reactive end group of the multifunctional crosslinker.

[0009] According to yet another exemplary embodiment, a method for making an ophthalmic device includes:

[0010] (a) curing a monomer mixture in a mold, the monomer mixture comprising:

[0011] (i) a multifunctional crosslinker comprising one or more repeat units of a siloxanyl group or a silyl-alkyl-siloxanyl group and containing at least two ethylenically unsaturated reactive end groups, one of which is a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group, and the other of which is an allyl-containing reactive end group or a vinyl-containing reactive end group;

[0012] (ii) one or more first ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with a (meth)acrylate-containing or acrylamide-containing reactive end group of the multifunctional crosslinker;

[0013] (iii) one or more second ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with an allyl- or vinyl-containing reactive end group of the multifunctional crosslinker; and

[0014] (b) drying and releasing the ophthalmic device from the mold. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Various exemplary embodiments described herein are directed to multifunctional crosslinkers and their use in forming ophthalmic devices such as contact lenses.

[0016] Ophthalmic devices such as contact lenses are prepared by polymerizing a lens-forming monomer mixture. Conventional polymer formulations contain two or more free radical monomers with two different reactivities and a single crosslinker that can provide a polymer in which the two monomers essentially coexist as two homopolymers. During the early stages of the polymerization reaction, one comonomer reacts preferentially with the crosslinker, and only after that comonomer is nearly consumed does the second comonomer begin to react with the crosslinker. In some cases, the large difference in reactivity between the crosslinker and the second comonomer can provide a polymer with a relatively large amount of unreacted second comonomer or oligomer that must then be extracted from the polymer.

[0017] For example, N-vinyl lactams such as N-vinyl-2-pyrrolidone (NVP) can be copolymerized with acrylate or methacrylate comonomers. However, N-vinyl lactams are known to be notoriously slow in free radical polymerization reactions with many of the more common acrylate, methacrylate, and acrylamide-based monomers. Such copolymers are difficult to synthesize in a homogeneous, controlled manner due to the difference in polymerization reaction rate between the N-vinyl group of NVP and the acryloyl or methacryloyl group of the acrylate or methacrylate comonomer. One such problem is that the difference in polymerization rate between the allyl or vinyl group of one comonomer and the methacrylate or acrylamide group of another comonomer can result in the allyl or vinyl monomer not being completely consumed while the methacrylate monomer is completely reacted. Thus, unreacted monomers can cause difficulties in the lens purification step and reduce the control of the lens formulation over the lens properties.

[0018] In addition, in this type of reaction, phase separation and a corresponding decrease in the transparency of the polymer lens material is typically observed, or the mechanical properties of the lens material deteriorate as the lens absorbs water. This is very inefficient in terms of production cost (yield) and can be detrimental to material properties. Also, it is often difficult to prepare the polymer from one production batch to another under such variable reaction conditions and stay within the design specifications. Therefore, there is a need for an improved ophthalmic device that overcomes the problems associated with copolymerizing at least two monomers with different reactivities.

[0019] The ophthalmic devices described herein advantageously overcome the aforementioned problems by reacting comonomers having different reactivities with a multifunctional crosslinker, resulting in an ophthalmic device having a relatively lower level of extractable materials than an ophthalmic device formed in the absence of the multifunctional crosslinker. Thus, the use of a multifunctional crosslinker in the ophthalmic device-forming monomer mixture avoids an extraction step after the formation of the ophthalmic device.

[0020] In non-limiting exemplary embodiments, the multifunctional crosslinker comprises one or more repeat units of one or more siloxanyl groups or one or more silyl-alkyl-siloxanyl groups and contains at least two ethylenically unsaturated reactive end groups, one of which is a (meth)acrylate-containing reactive end group or a (meth)acrylamide-containing reactive end group and the other of which is an allyl-containing reactive end group or a vinyl-containing reactive end group.

[0021] As used herein, the term "(meth)" refers to an optional methyl substituent. Thus, a term such as "(meth)acrylate" refers to either a methacrylate or an acrylate, and "(meth)acrylamide" refers to either a methacrylamide or an acrylamide.

[0022] In non-limiting exemplary embodiments, the multifunctional crosslinker comprises one or more repeat units of a siloxanyl group. In one exemplary embodiment, the multifunctional crosslinker comprises from about 3 to about 300 repeat units of a siloxanyl group. In another exemplary embodiment, the multifunctional crosslinker comprises from about 3 to about 90 repeat units of a siloxanyl group. In one exemplary embodiment, the siloxanyl group is represented by the following structure: [ka] R 1 and R 2 are independently hydrogen, C1 to C 12 Alkyl groups, C1-C 12 Haloalkyl groups, C3-C 12 Cycloalkyl groups, C3-C 12 Heterocycloalkyl groups, C2-C 12 Alkenyl group, haloalkenyl group, or C6-C 12 It is an aromatic group, and y is 3 to about 300, or 3 to about 90.

[0023] In an exemplary embodiment, the multifunctional crosslinker containing one or more repeating units of siloxanyl groups can be obtained by a stepwise anionic polymerization reaction.For example, in one exemplary embodiment, the repeating unit of siloxanyl groups can be derived in a first step by a ring-opening polymerization reaction between 1,1,4,4-tetramethyl-1,4-disila-5-oxacyclopentane (EDS) and a first monomer having a first reactive functional group, such as a hydroxyl group, for reacting with EDS, and a second reactive functional group that is one of at least two ethylenically unsaturated reactive end groups, optionally in the presence of an organic catalyst.

[0024] In an exemplary embodiment, the first step of the reaction is carried out at a temperature ranging from about 0 to about 100° C. for a period ranging from about 1 minute to about 24 hours. In an exemplary embodiment, the first monomer is added to the reaction mixture in an amount ranging from about 2 to about 20% by weight, based on the total weight of the mixture. In an exemplary embodiment, EDS is added to the reaction mixture in an amount ranging from about 5 to about 95% by weight, based on the total weight of the mixture.

[0025] Suitable first monomers for reacting with the EDS compound include, for example, allyl C1-C6 alkanols such as allyl alcohol; allyloxy C1-C6 alkanols such as allyloxymethanol, allyloxyethanol, allyloxypropanol, and the like; (hydroxydimethylsilyl) C1-C6 alkyl methacrylates such as (hydroxydimethylsilyl)methyl methacrylate, (hydroxydimethylsilyl)ethyl methacrylate, (hydroxydimethylsilyl)propyl methacrylate, and the like; and alkali metal allyldimethylsilanolates such as potassium allyldimethylsilanolate.

[0026] Suitable organic catalysts include, for example, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,3 bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, and 1,3,4,5-tetramethylimidazol-2-ylidene. In an exemplary embodiment, the organic catalyst is added to the reaction mixture in an amount ranging from about 0.01 to about 20% by weight, based on the total weight of the mixture.

[0027] The ring-opening polymerization reaction product obtained in the first step is then reacted with a second monomer having a first reactive functional group for reacting with the ring-opening polymerization reaction product and a second reactive functional group that is the other of the at least two ethylenically unsaturated reactive end groups to form a multifunctional crosslinker. Suitable second monomers include, for example, (dimethylchlorosilyl)alkyl methacrylates such as 3-(dimethylchlorosilyl)methyl methacrylate, 3-(dimethylchlorosilyl)ethyl methacrylate, 3-(dimethylchlorosilyl)propyl methacrylate, etc., allyldimethylchlorosilane, etc.

[0028] In an exemplary embodiment, the second step of the reaction is carried out at a temperature ranging from about 0 to about 100° C. for a period ranging from about 1 minute to about 24 hours. In an exemplary embodiment, the second monomer is added to the reaction mixture in an amount ranging from about 2 to about 20 weight percent, based on the total weight of the mixture. In an exemplary embodiment, the ring-opening polymerization reaction product is added to the reaction mixture in an amount ranging from about 5 to about 95 weight percent, based on the total weight of the mixture.

[0029] Various synthetic schemes for obtaining polyfunctional crosslinkers containing one or more repeating units of siloxanyl groups are presented below. [ka]

[0030] In a non-limiting exemplary embodiment, the multifunctional crosslinker comprises one or more repeat units of a silyl-alkyl-siloxanyl group. In one exemplary embodiment, the multifunctional crosslinker comprises from about 1 to about 100 repeat units of a silyl-alkyl-siloxanyl group. In another exemplary embodiment, the multifunctional crosslinker comprises from about 1 to about 30 repeat units of a silyl-alkyl-siloxanyl group. The alkyl group of the silyl-alkyl-siloxanyl group can be an alkyl group having from 2 to about 4 carbon atoms or about 2 carbon atoms. In one exemplary embodiment, the silyl-alkyl-siloxanyl group is represented by the following structure: [ka] R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently hydrogen, C1 to C 12 Alkyl groups, haloalkyl groups, C3-C 12 Cycloalkyl groups, C3-C 12 Heterocycloalkyl groups, C2-C 12 Alkenyl group, haloalkenyl, or C6-C 12 It is an aromatic group, a is 2 to 4, and x is 1 to about 100 or 1 to about 30.

[0031] In an exemplary embodiment, the multifunctional crosslinker containing one or more repeating units of silyl-alkyl-siloxanyl group can be obtained by stepwise anionic polymerization reaction as described above.For example, in one exemplary embodiment, the silyl-alkyl-siloxanyl group can be derived in a first step by ring-opening polymerization reaction between hexamethylcyclotrisiloxane and a first monomer having a first reactive functional group, such as a hydroxyl group, for reacting with hexamethylcyclotrisiloxane, and a second reactive functional group that is one of at least two ethylenically unsaturated reactive end groups, optionally in the presence of an organic catalyst.

[0032] The first monomer and organic catalyst and the amounts thereof used in the reaction can be the same as those discussed hereinabove. In addition, the reaction conditions for the first step can be the same as those discussed hereinabove.

[0033] In an exemplary embodiment, the amount of hexamethylcyclotrisiloxane used in the reaction mixture can range from about 10 to about 95 weight percent, based on the total weight of the mixture.

[0034] The ring-opening polymerization reaction product from the first step is then reacted with a second monomer having a first reactive functional group for reacting with the ring-opening polymerization reaction product and a second reactive functional group that is the other of the at least two ethylenically unsaturated reactive end groups to form a multifunctional crosslinker.

[0035] The suitable second monomer and the amount used, as well as the amount of the ring-opening polymerization reaction product in the reaction, may be the same as those discussed hereinabove. In addition, the reaction conditions of the second step may be the same as those discussed hereinabove.

[0036] Various synthetic schemes for obtaining multifunctional crosslinkers containing one or more repeat units of silyl-alkyl-siloxanyl groups are shown below. [ka]

[0037] In exemplary embodiments, the ethylenically unsaturated reactive end groups include, by way of example, (meth)acrylate end groups, vinyl end groups, acrylamide end groups, and the like. In one embodiment, the ethylenically unsaturated reactive end group is a methacrylate-containing reactive end group. Suitable methacrylate-containing reactive end groups may be represented by the following structure: [ka] R* is a linking group or bond. Suitable linking groups include, for example, any divalent hydrocarbon radical or moiety, such as, independently, linear or branched, substituted or unsubstituted C1-C6 alkyl groups, substituted or unsubstituted C3-C6 alkyl groups, substituted or unsubstituted C4-C6 alkyl groups, substituted or unsubstituted C5-C6 alkyl groups, substituted or unsubstituted C6-C7 alkyl groups, substituted or unsubstituted C7-C8 alkyl groups, substituted or unsubstituted C8-C9 alkyl groups, substituted or unsubstituted C9-C10 alkyl groups, substituted or unsubstituted C10-C12 ... 12 Cycloalkyl groups, substituted or unsubstituted C4-C 12 Cycloalkylalkyl groups, substituted or unsubstituted C3-C 12 Cycloalkenyl groups, substituted or unsubstituted C6-C 12 Aryl groups, substituted or unsubstituted C7-C 12 Included are arylalkyl groups, and substituted or unsubstituted ether-containing groups.

[0038] According to another exemplary embodiment, an ophthalmic device that is a polymerization product of a monomer mixture comprising:

[0039] (a) one or more multifunctional crosslinkers described herein; and

[0040] (b) one or more first ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with a (meth)acrylate-containing or acrylamide-containing reactive end group of the multifunctional crosslinker;

[0041] (c) one or more second ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with the allyl- or vinyl-containing reactive end group of the multifunctional crosslinker.

[0042] The ophthalmic devices described herein are intended to be in direct contact with body tissues or fluids. As used herein, the term "ophthalmic device" refers to devices that reside in and on the eye. These ophthalmic devices can provide optical correction, wound treatment, drug delivery, diagnostic functions, or cosmetic enhancements or effects, or a combination of these properties. Useful ophthalmic devices include, but are not limited to, ophthalmic lenses, such as soft contact lenses, e.g., soft hydrogel soft lenses, soft non-hydrogel soft lenses, hard contact lenses, e.g., hard gas permeable lens materials, intraocular lenses, overlay lenses, intraocular inserts, optical inserts, and the like. As will be understood by those skilled in the art, a lens is considered to be "soft" if it can fold back on itself without breaking.

[0043] In an exemplary embodiment, one or more multifunctional crosslinkers described herein are present in the monomer mix in an ophthalmic device forming amount. In one embodiment, one or more multifunctional crosslinkers described herein are present in the monomer mix in an amount of about 1 to about 50% by weight, based on the total weight of the monomer mix. In another embodiment, one or more multifunctional crosslinkers described herein are present in the monomer mix in an amount of about 1 to about 30% by weight, based on the total weight of the monomer mix.

[0044] In an exemplary embodiment, the first ophthalmic device-forming comonomer is an ophthalmic device-forming comonomer having at least one reactive group capable of preferentially reacting with a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group. In a non-limiting exemplary embodiment, the first ophthalmic device-forming comonomer is one or more silicone ophthalmic device-forming comonomers.

[0045] In an exemplary embodiment, a suitable silicone ophthalmic device forming comonomer is a compound represented by the structure of Formula I: [ka] where V is an ethylenically unsaturated polymerizable group, L is a linker group or a bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently H, C1 to C 12 Alkyl groups, haloalkyl groups, C3-C 12 Cycloalkyl groups, heterocycloalkyl groups, C2-C 12 Alkenyl group, haloalkenyl group, or C6-C 12 is an aromatic group, R 10 and R 11 are independently H or C1-C 12 is an alkyl group, R 10 and R11 at least one of which is hydrogen, y is 2 to 7, and n is 1 to 100, or 1 to 20.

[0046] Suitable ethylenically unsaturated polymerizable groups include, for example, (meth)acrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl carbamates, and (meth)acrylamides.

[0047] The linker group can be any divalent radical or moiety, for example, a substituted or unsubstituted C1-C 12 These include alkyl groups, alkyl ether groups, alkenyl groups, alkenyl ether groups, haloalkyl groups, substituted or unsubstituted siloxane groups, and monomers capable of propagating ring opening.

[0048] In one embodiment, V is a (meth)acrylate and L is a C1-C 12 is an alkylene group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independent, C1~C 12 is an alkyl group, R 10 and R 11 is independently H, y is 2 to 7, and n is 3 to 8.

[0049] In one embodiment, V is a (meth)acrylate, L is a C1-C6 alkyl group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently a C1 to C6 alkyl group, and R 10 and R 11is independently H, y is 2 to 7, and n is 1 to 20.

[0050] Non-bulky organosilicon-containing monomers represented by the structure of Formula I are known in the art, see, for example, U.S. Pat. Nos. 7,915,323, 7,994,356, 8,420,711, 8,827,447, and 9,039,174, the contents of which are incorporated herein by reference.

[0051] In an exemplary embodiment, suitable silicone ophthalmic device-forming comonomers are non-bulky organosilicon-containing monomers including compounds represented by the structure of Formula II: [ka] In the formula, R 12 is H or methyl, and X is O or NR 16 and R 16 is selected from H or a C1-C4 alkyl group, which may be further substituted with one or more hydroxyl groups, and in some embodiments is H or methyl; R 13 is a divalent alkyl group which may be further functionalized with a group selected from the group consisting of ether groups, hydroxyl groups, carbamate groups, and combinations thereof, and in another embodiment is a C1-C6 alkylene group which may be substituted with ethers, hydroxyls, and combinations thereof, and in yet another embodiment is a C1 or C3-C4 alkylene group which may be substituted with ethers, hydroxyls, and combinations thereof; each R 14 is independently phenyl or C1-C4 alkyl, which may be substituted with fluorine, hydroxyl, or ether; in another embodiment, each R 14 is independently selected from ethyl and methyl groups, and in another embodiment, each R 14 is methyl, R 15 is a C1-C4 alkyl group and a is 2-50, and in some embodiments, 5-15.

[0052] Non-bulky organosilicon-containing monomers represented by the structure of formula II are known in the art, see, for example, U.S. Pat. Nos. 8,703,891, 8,937,110, 8,937,111, 9,156,934, and 9,244,197, the contents of which are incorporated herein by reference.

[0053] Representative examples of non-bulky organosilicon-containing monomers represented by the structure of Formula II include the following:

[0054] M1EDS6: A compound having the following structure and available from Gelest: [ka]

[0055] MCR-M11: a compound having the following structure: [ka]

[0056] M1-MCR-C12: a compound having the following structure: [ka] (n is 12 on average).

[0057] In an exemplary embodiment, a suitable silicone ophthalmic device-forming comonomer is a polysiloxane prepolymer represented by the structure of Formula III: [ka] wherein each V is independently a reactive functional end group, examples of which include hydroxyl-containing reactive functional end groups, and amine-containing reactive functional end groups; R 17 ~R 22 are independently linear or branched, substituted or unsubstituted C1-C 30Alkyl groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C4-C 30 Cycloalkylalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C6-C 30 Aryl groups, and substituted or unsubstituted C7-C 30 It comprises an arylalkyl group, and L is independently a linking group.

[0058] Hydroxyl-containing reactive functional end groups for use herein are groups of the general formula -OH. Representative examples of amine-containing reactive functional end groups for use herein include, by way of example, the following general formula -NHR 23 and wherein R 23 is independently hydrogen or an alkyl group, an aryl group, a cycloalkyl group, and the like, as defined herein.

[0059] The linking groups L are independently straight or branched chain alkyl groups, cycloalkyl groups, aryl groups, ether or polyether groups, and ester groups as defined herein.

[0060] Representative examples of alkyl groups for use herein include, by way of example, straight or branched alkyl chain radicals containing carbon and hydrogen atoms of 1 to about 30 carbon atoms, or 1 to about 12 carbon atoms, or 1 to about 6 carbon atoms, relative to the remainder of the molecule, with or without unsaturation, such as methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, methylene, ethylene, and the like, and optionally containing one or more heteroatoms, such as O and N.

[0061] Representative examples of cycloalkyl groups for use herein include, by way of example, substituted or unsubstituted non-aromatic monocyclic or polycyclic ring systems of about 3 to about 30 carbon atoms, or 3 to about 12 carbon atoms, or 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronaphthyl, adamantyl, and norbornyl groups, bridged cyclic or spiro bicyclic groups, such as spiro-(4,4)-non-2-yl, and the like, optionally containing one or more heteroatoms, such as O and N.

[0062] Representative examples of cycloalkylalkyl groups for use herein include, by way of example, substituted or unsubstituted cyclic ring-containing radicals containing from about 4 to about 30 carbon atoms, or from 3 to about 6 carbon atoms, which are bonded directly to an alkyl group and then attached to the main structure of the monomer at any carbon from the alkyl group to form a stable structure, e.g., cyclopropylmethyl, cyclobutylethyl, cyclopentylethyl, and the like, and the cyclic ring may optionally contain one or more heteroatoms, such as O and N.

[0063] Representative examples of cycloalkenyl groups for use herein include, by way of example, substituted or unsubstituted cyclic ring-containing groups containing from about 3 to about 30 carbon atoms, or from 3 to about 6 carbon atoms, and having at least one carbon-carbon double bond, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and the like, wherein the cyclic ring may optionally contain one or more heteroatoms, such as O and N.

[0064] Representative examples of aryl groups for use herein include, by way of example, substituted or unsubstituted monocyclic or polycyclic aromatic radicals containing from about 6 to about 30 carbon atoms, or from about 6 to about 12 carbon atoms, such as phenyl, naphthyl, tetrahydronaphthyl, indenyl, biphenyl, and the like, optionally containing one or more heteroatoms, such as O and N.

[0065] Representative examples of arylalkyl groups for use herein include, by way of example, a substituted or unsubstituted aryl group, as defined herein, directly bonded to an alkyl group, as defined herein, such as, for example, -CH2C6H5, -C2H4C6H5, and the like, where the aryl group may optionally contain one or more heteroatoms, such as, for example, O and N.

[0066] Representative examples of ester groups for use herein include, by way of example, carboxylic acid esters having 1 to 20 carbon atoms.

[0067] Representative examples of ether- or polyether-containing groups for use herein include, by way of example, alkyl ethers, cycloalkyl ethers, cycloalkylalkyl ethers, cycloalkenyl ethers, aryl ethers, arylalkyl ethers, where alkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, aryl, and arylalkyl groups are as defined herein. Exemplary ether- or polyether-containing groups include, by way of example, alkylene oxides, poly(alkylene oxides), such as ethylene oxide, propylene oxide, butylene oxide, poly(ethylene oxide), poly(ethylene glycol), poly(propylene oxide), poly(butylene oxide), and mixtures or copolymers thereof, alkylene oxides of the general formula -(R 14 OR 15 ) t ether or polyether group, 14 is a bond, a substituted or unsubstituted alkyl, cycloalkyl, or aryl group as defined herein; R 15 is a substituted or unsubstituted alkyl, cycloalkyl, or aryl group as defined herein, and t is at least 1.

[0068] Representative examples of polysiloxane prepolymers are as follows: [ka]

[0069] Methods for making the polysiloxane prepolymers described herein are well known and within the purview of those skilled in the art. Additionally, polysiloxane prepolymers are also commercially available from sources such as, for example, Gelest, Silar, Shin-Etsu, Momentive, and Siltech.

[0070] In an exemplary embodiment, a suitable silicone ophthalmic device-forming comonomer is a bulky siloxane monomer represented by the structure of formula IV: [ka] In the formula, X is -O- or -NR 19 - represents R 19 is hydrogen or a C1-C4 alkyl group, and each R 17 each independently represents hydrogen or methyl; 18 represents independently a lower alkyl radical, such as a C1-C6 alkyl radical, a phenyl radical, or a group represented by [ka] Each R 18’ independently represents a lower alkyl, such as a C1-C6 alkyl, or a phenyl radical; and h is 1-10.

[0071] In an exemplary embodiment, a suitable silicone ophthalmic device-forming comonomer is a bulky siloxane monomer represented by the structure of Formula V: [ka] In the formula, X is -NR 19 - represents R 19 represents hydrogen or a C1-C4 alkyl group, R 17 represents hydrogen or methyl, and each R 18represents independently a lower alkyl radical, such as C1-C6 alkyl, a phenyl radical, or a group represented by [ka] Each R 18’ independently represents a lower alkyl, such as a C1-C6 alkyl, or a phenyl radical; and h is 1-10.

[0072] Representative examples of the one or more bulky siloxane monomers include, for example, methacryloxypropyl tris(trimethylsiloxy)silane (TRIS), pentamethyldisiloxanylmethyl methacrylate, tris(trimethylsiloxy)methacryloxypropyl silane, phenylthreitolmethyldisiloxanylethyl acrylate, methyldi(trimethylsiloxy)methacryloxymethylsilane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate (TRIS-VC), 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, and mixtures thereof.

[0073] In an exemplary embodiment, the first ophthalmic device-forming comonomer may be present in the monomer mixture in an amount ranging from about 1% to about 80% by weight, based on the total weight of the monomer mixture. In an exemplary embodiment, the first ophthalmic device-forming comonomer may be present in the monomer mixture in an amount ranging from about 1% to about 60% by weight, based on the total weight of the monomer mixture.

[0074] In an exemplary embodiment, the second ophthalmic device-forming comonomer having at least one reactive group that can preferentially react with the allyl-containing or vinyl-containing reactive end group of the multifunctional crosslinker is a hydrophilic ophthalmic device-forming comonomer. Thus, in one non-limiting exemplary embodiment, the hydrophilic monomer is an N-vinyl lactam selected from the group consisting of N-vinyl pyrrolidone (NVP), N-vinyl piperidone, and N-vinyl-ε-caprolactam, and mixtures thereof. Other suitable hydrophilic vinyl monomers include N-vinyl imidazolidone, N-vinyl succinimide, and N-vinyl formamide. In an exemplary embodiment, the second ophthalmic device-forming comonomer is NVP.

[0075] In other non-limiting exemplary embodiments, the hydrophilic comonomers can include one or more of unsaturated carboxylic acids, amides, polymerizable amines, vinyl carbonates, vinyl carbamates, oxazolone monomers, copolymers thereof, and the like, and mixtures thereof. Useful amides include acrylamides, such as N,N-dimethylacrylamide and N,N-dimethylmethacrylamide. Other examples of hydrophilic comonomers include hydrophilic prepolymers, such as poly(alkene glycols), functionalized with polymerizable groups. Useful examples of functionalized poly(alkene glycols) include poly(diethylene glycols) of various chain lengths containing monomethacrylate or dimethacrylate end caps. In embodiments, the poly(alkene glycol) polymer contains at least two alkene glycol monomer units. Yet further examples are the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Pat. No. 5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277. Other suitable hydrophilic monomers will be apparent to those skilled in the art.

[0076] In an exemplary embodiment, the second ophthalmic device-forming comonomer may be present in the monomer mixture in an amount ranging from about 1% to about 80% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, the second ophthalmic device-forming comonomer may be present in the monomer mixture in an amount ranging from about 1% to about 60% by weight, based on the total weight of the monomer mixture.

[0077] In a non-limiting exemplary embodiment, the monomer mixture can further comprise one or more hydrophobic monomers.Suitable hydrophobic monomers include ethylenically unsaturated hydrophobic monomers, such as (meth)acrylate-containing hydrophobic monomers, N-alkyl (meth)acrylamide-containing hydrophobic monomers, alkyl vinyl carbonate-containing hydrophobic monomers, alkyl vinyl carbamate-containing hydrophobic monomers, fluoroalkyl (meth)acrylate-containing hydrophobic monomers, N-fluoroalkyl (meth)acrylamide-containing hydrophobic monomers, N-fluoroalkyl vinyl carbonate-containing hydrophobic monomers, N-fluoroalkyl vinyl carbamate-containing hydrophobic monomers, silicone-containing (meth)acrylate-containing hydrophobic monomers, (meth)acrylamide-containing hydrophobic monomers, vinyl carbonate-containing hydrophobic monomers, vinyl carbamate-containing hydrophobic monomers, styrene-containing hydrophobic monomers, and polyoxypropylene (meth)acrylate-containing hydrophobic monomers, and mixtures thereof.

[0078] In an exemplary embodiment, the one or more hydrophobic monomers are represented by the structure of Formula VI: [ka] In the formula, R 1 is methyl or hydrogen, R 2 is -O- or -NH-, R 3 and R 4 are independently -CH2-, -CHOH-, and -CHR 6 -, R 5 and R 6are independently a branched C3 to C8 alkyl group, R 7 is hydrogen or —OH; n is an integer of at least 1; and m and p are independently 0 or integers of at least 1, with the proviso that the sum of m, p, and n is 2, 3, 4, or 5.

[0079] Representative examples of the one or more hydrophobic monomers represented by the structure of formula VI include, but are not limited to, 4-t-butyl-2-hydroxycyclohexyl methacrylate (TBE), 4-t-butyl-2-hydroxycyclopentyl methacrylate, 4-t-butyl-2-hydroxycyclohexyl methacrylamide (TBA), 6-isopentyl-3-hydroxycyclohexyl methacrylate, 2-isohexyl-5-hydroxycyclopentyl methacrylamide, 4-t-butylcyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, benzyl methacrylate, etc. In one embodiment, the one or more hydrophobic monomers (b) comprise a compound of formula VI, wherein R 3 is -CH2-, m is 1 or 2, p is 0, and the sum of m and n is 3 or 4.

[0080] In an exemplary embodiment, the one or more hydrophobic monomers will be present in the monomer mixture in an amount ranging from about 0.5 to about 25 weight percent, based on the total weight of the monomer mixture, hi another exemplary embodiment, the one or more hydrophobic monomers will be present in the monomer mixture in an amount ranging from about 1 to about 10 weight percent, based on the total weight of the monomer mixture.

[0081] The monomer mixture may further contain various additives such as antioxidants, wetting agents, reinforcing agents, and other additives well known in the art, as necessary, within the scope of the present disclosure.

[0082] Suitable wetting agents include, for example, glycerin, propylene glycol, mono- or disaccharides, polyethylene glycol, ethoxylated glucose, and combinations thereof. In one embodiment, suitable wetting agents may be polymers containing carboxylic acid functionality, such as polymers containing polyacrylic acid (PAA). Specific coating wetting agents include P(vinylpyrrolidinone) (PVP)-co-acrylic acid (AA), P(methyl vinyl ether-alt-maleic acid), P(acrylic acid-graft-ethylene oxide), P(acrylic acid-co-methacrylic acid), P(acrylamide-co-AA), P(acrylamide-co-AA), P(AA-co-maleic), P(butadiene-maleic acid), and P(N-vinylpyrrolidone-co-vinyl acetate), and polyvinyl alcohol.

[0083] In another exemplary embodiment, the monomer mixture further comprises one or more ultraviolet (UV) blocking agents. In one exemplary embodiment, suitable UV blocking agents include, for example, those represented by the following formula: [ka] (2-propenoic acid, 2-methyl, 2-(4-benzoyl-3-hydroxyphenoxy)-1-[(4-benzoyl 3-hydroxyphenoxy)methyl ester), [ka] These compounds are merely exemplary and are not intended to be limiting. Any known or subsequently developed UV blocking agent is contemplated for use herein.

[0084] Exemplary embodiment ophthalmic devices, e.g., contact lenses or intraocular lenses, can be prepared by polymerizing the monomer mixture described above to form a product that can then be formed into the appropriate shape, e.g., by lathing, injection molding, compression molding, cutting, etc. For example, in manufacturing contact lenses, the initial mixture may be polymerized in a tube to provide rod-like articles that are then cut into buttons. The buttons may then be lathed into contact lenses.

[0085] Alternatively, ophthalmic devices such as contact lenses may be poured directly from the mixture into a mold, e.g., a polypropylene mold, by, for example, spin casting and static casting. Spin casting is disclosed in U.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting is disclosed in U.S. Pat. Nos. 4,113,224, 4,197,266, and 5,271,875. Spin casting involves filling a mold with the mixture to be polymerized and rotating the mold in a controlled manner while exposing the mixture to a radiation source, such as UV light. Static casting involves filling a monomer mixture between two mold parts, one mold part shaped to form the anterior surface of the lens and the other mold part shaped to form the posterior surface of the lens, and curing the mixture while held in the mold assembly to form a lens, e.g., by free radical polymerization of the mixture. Examples of free radical reaction techniques for curing lens materials include thermal radiation, infrared radiation, electron beam radiation, gamma radiation, and ultraviolet (UV) radiation, or a combination of such techniques may be used. US Patent No. 5,271,875 describes a static casting method that allows for the molding of a finished lens in a mold cavity defined by a back mold and a front mold. As an additional method, US Patent No. 4,555,732 discloses a process in which an excess of a monomer mixture is cured by spin casting in a mold to form a molded article having a lens anterior surface and a relatively large thickness, and the posterior surface of the cured spin cast article is then latched to provide a contact lens having a desired thickness and lens posterior surface.

[0086] Polymerization may be promoted by exposing the monomer mixture to heat and / or radiation, such as ultraviolet light, visible light, or high-energy radiation. A polymerization initiator may be included in the mixture to promote the polymerization step. Representative examples of free radical thermal polymerization initiators include organic peroxides, such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, peroxypivalate, and peroxydicarbonate. Representative UV initiators are 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. Generally, initiators will be used in the monomer mixture at a concentration of from about 0.01 to about 5 weight percent of the total mixture.

[0087] The polymerization can be carried out in a reaction medium such as a solution or dispersion using a solvent such as tetrahydrofuran or toluene. Alternatively, the polymerization can be a bulk polymerization.

[0088] Generally, the polymerization can be carried out under an inert atmosphere of, for example, nitrogen or argon, for about 15 minutes to about 72 hours. If desired, the resulting polymerization product can be dried under vacuum, for example, for about 5 to about 72 hours, or left in an aqueous solution before use.

[0089] Polymerization of the mixture results in a polymer that, when hydrated, preferably forms a hydrogel. When producing hydrogel lenses, the mixture may further include at least one diluent that will eventually be replaced by water when the polymerization product is hydrated to form a hydrogel. Generally, the water content of the hydrogel is as described hereinabove, i.e., at least about 45 weight percent, or at least about 50 weight percent. The amount of diluent used should be less than about 50 weight percent, and in most cases the diluent content will be less than about 30 weight percent. However, for a particular polymer system, the practical limit will be determined by the solubility of the various monomers in the diluent. To produce optically clear copolymers, it is important that no phase separation occurs between the comonomer and the diluent, or between the diluent and the final copolymer, which would result in visual opacity.

[0090] Additionally, the maximum amount of diluent that can be used will depend on the amount of swelling that the diluent causes to the final polymer. Excessive swelling can cause or disintegrate the copolymer when the diluent is replaced by water upon hydration. Suitable diluents include, but are not limited to, ethylene glycol, glycerin, liquid poly(ethylene glycol), alcohol, alcohol / water mixtures, ethylene oxide / propylene oxide block copolymers, low molecular weight linear poly(2-hydroxyethyl methacrylate), glycol esters of lactic acid, formamides, ketones, dialkyl sulfoxides, butyl carbitol, borate esters of polyhydric alcohols such as borate esters of glycerol, and the like, and mixtures thereof.

[0091] It may be desirable to remove residual diluent from the lens prior to the edge finishing operation, which can be accomplished by evaporation at or near ambient pressure, or under vacuum, if desired. High temperatures can be used to reduce the time required to evaporate the diluent. The time, temperature, and pressure conditions for the solvent removal step will vary depending on factors such as the volatility of the diluent and the particular monomeric components, as can be readily determined by one of ordinary skill in the art. If desired, the mixture used to make hydrogel lenses may further include crosslinkers and wetting agents known in the prior art for making hydrogel materials.

[0092] In the case of intraocular lenses, the monomer mixture to be polymerized may further include a monomer to increase the refractive index of the resulting polymerization product. Examples of such monomers include aromatic (meth)acrylates, such as phenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 2-phenoxyethyl methacrylate, and benzyl (meth)acrylate.

[0093] The ophthalmic devices, such as contact lenses, obtained herein may be subjected to optional machining operations. For example, other optional machining steps may include buffing or polishing the edges and / or surfaces of the lens. Generally, such machining processes may be performed before or after the product is released from the mold parts, for example, the lens is dry demolded from the mold by lifting the lens from the mold with vacuum tweezers, after which the lens is transferred by 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 flipped over to machine the other side of the lens.

[0094] The lenses may then be transferred to individual lens packages containing a buffered saline solution. Saline may be added to the package either before or after transfer of the lenses. Suitable package designs and materials are known in the art. The plastic package is peelably sealed with a film. Suitable sealing films are known in the art and include foils, polymeric films, and mixtures thereof. The sealed package containing the lenses is then sterilized to ensure a sterile product. Suitable sterilization means and conditions are known in the art and include, for example, autoclaving.

[0095] As one of ordinary skill in the art would readily appreciate, other steps can be included in the above-described molding and packaging process, including, for example, coating the formed lenses, surface treating the lenses during formation (e.g., via mold transfer), inspecting the lenses, discarding defective lenses, cleaning mold halves, and reusing mold halves, as well as combinations thereof.

[0096] The following examples are provided to enable one of ordinary skill in the art to practice the invention and are merely illustrative and should not be read as limiting the scope of the invention as defined by the claims.

[0097] In the examples, the following abbreviations are used:

[0098] TBD: 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0099] EDS: 1,1,4,4-tetramethyl-1,4-disila-5-oxacyclopentane.

[0100] D3: Hexamethylcyclotrisiloxane.

[0101] DMA: N,N-dimethylacrylamide.

[0102] HEMA: 2-hydroxyethyl methacrylate.

[0103] NVP: N-vinyl-2-pyrrolidone.

[0104] EGDMA: ethylene glycol dimethacrylate.

[0105] TRIS: 3-[tris(trimethylsiloxy)silyl]propyl methacrylate.

[0106] UV416: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate.

[0107] Irgacure 819: Photoinitiator for free radical polymerization available from Sigma Aldrich.

[0108] IMVT: 1,4-bis(4-(2-methacryloxyethyl)phenylamino)anthraquinone.

[0109] IPA: Isopropyl alcohol.

[0110] Ma2D37: A compound having the following structure and available from Shin-Etsu and Gelest: [ka]

[0111] M1EDS6: A compound having the following structure and available from Gelest: [ka]

[0112] As discussed below, various polymerization products were formed and characterized by standard test procedures as follows.

[0113] Moisture content: Two sets of six hydrated lenses or films are blotted dry on a piece of filter paper to remove excess water and the samples are weighed (wet weight). The samples are then placed in a jar containing desiccant and heated in a microwave oven for 10 minutes. The samples are then allowed to stand for 30 minutes to equilibrate to room temperature and reweighed (dry weight). The moisture content is calculated from the wet and dry weights.

[0114] Contact angle: Captive bubble contact angle data was collected on a First Ten Angstroms FTA-1000 prop Shape Instrument. All samples were rinsed in HPLC grade water prior to analysis to remove components of the packaging solution from the sample surface. Prior to data collection, the surface tension of the water used for all experiments was measured using the pendant drop method. Surface tension values ​​of 70-72 dynes / cm were expected for the water to be deemed suitable for use. All lens samples were placed on a curved sample holder and submerged in a quartz cell filled with HPLC grade water. Advancing and receding captive bubble contact angles were collected for each specimen. The advancing contact angle is defined as the angle measured in water as the bubble is receding from the lens surface (water is advancing across the surface). All captive bubble data was collected using a high speed digital camera focused on the sample / bubble interface. Contact angles were calculated in digital frames just prior to the contact line movement across the sample / bubble interface. The receding contact angle is defined as the angle measured in water when an air bubble is swelling across the sample surface (the water is receding from the surface).

[0115] The film samples were immersed in borate buffered saline and the elastic modulus (g / mm) was measured according to ASTM 1708 using an Instron (Model 4502) instrument. 2 ) was measured, the approximate size of the film sample was 22 mm gauge length and 4.75 mm width, the sample further had ends forming a dog bone shape to accommodate gripping of the sample by the clamps of the Instron instrument, and was 100±50 microns thick.

[0116] Extractables Test, PVP, and Silicone: The resulting monomer mixture was cast into contact lenses by introducing the monomer mixture into a polypropylene mold assembly. The mold assembly and monomer mixture were then UV cured for about -0.5 hours to form contact lenses. The lenses were dry demolded and submitted directly to extractables test. The lenses were extracted with hot IPA in a Soxhlet extraction for 24 hours. The collected IPA was concentrated and submitted to HPLC analysis to determine the weight ratio of the extractables components.

[0117] UV-Vis Transmittance: Lenses were individually placed on a horizontal integrating sphere for contact lens measurements. Transmittance spectra were obtained from 200 nm to 800 nm.

[0118] Example 1 Allyl-(EDS) 10 - Preparation of M1 (n=10) crosslinker according to the following reaction scheme: [ka]

[0119] A 100 mL flask equipped with a stirrer was dried under vacuum using a heat gun. Anhydrous toluene (40 mL) was injected into the flask using a syringe. The flask was transferred to a nitrogen filled glove box. TBD (868 mg, 6.24 mmol, 1 equiv.) and allyl alcohol (434 mg, 7.48 mmol, 1.2 equiv.) were then added to the flask in the glove box. The flask was removed from the glove box. After the solution was stirred for 15 min, EDS (10 g, 62.4 mmol, 10 equiv.) was injected into the solution using a syringe. The mixture was stirred for 30 min. Then, 3-(dimethylchlorosilyl)propyl methacrylate (1790 mg, 8.1 mmol, 1.3 equiv.) and anhydrous pyridine (987 mg, 12.5 mmol, 2 equiv.) were added to the solution. The solution was stirred overnight. The solution was washed with 10% sodium bicarbonate solution (50 mL) and the organic layer was collected and concentrated. The concentrated solution was precipitated three times into methanol and the bottom layer was collected and dried under vacuum to give allyl-(EDS) as a clear viscous liquid (8.5 g). 10 -M1 was obtained.

[0120] Example 2 Allyl-(D3) was synthesized using the general synthetic procedure of Example 1, except that the EDS monomer was replaced with the D3 monomer. 10 -M1 crosslinker was obtained.

[0121] Example 3 Allyl-EO1-(EDS) 10 - Preparation of M1 (n=10) crosslinker according to the following reaction scheme: [ka]

[0122] A 100 mL flask equipped with a stirrer was dried under vacuum using a heat gun. Anhydrous toluene (20 mL) was injected into the flask using a syringe. The flask was transferred to a nitrogen filled glove box. Then, TBD (556 mg, 4 mmol, 1 equiv) and 2-aryoxyethanol (490 mg, 4.8 mmol, 1.2 equiv) were added to the flask in the glove box. The flask was removed from the glove box. After the solution was stirred for 15 minutes, EDS (6.4 g, 40 mmol, 10 equiv) was injected into the solution using a syringe. The mixture was allowed to stir for 30 minutes. Then, 3-(dimethylchlorosilyl)propyl methacrylate (1148 mg, 5.2 mmol, 1.3 equiv) and anhydrous pyridine (633 mg, 8 mmol, 2 equiv) were added to the solution. The solution was stirred overnight. The solution was washed with water (50 mL) and the organic layer was collected and concentrated. The concentrated solution was precipitated three times in methanol, and the bottom layer was collected and dried under vacuum to give allyl-EO1-(EDS) as a clear viscous liquid (3.9 g). 10 -M1 was obtained.

[0123] Example 4 Allyl-EO1-(D3) was synthesized using the general synthetic procedure of Example 3, except that the EDS monomer was replaced with the D3 monomer. 10 -M1 crosslinker was obtained.

[0124] Example 5 VS-(EDS) 90 - Preparation of M1 (n=90) crosslinker according to the following reaction scheme: [ka]

[0125] A 200 mL flask equipped with a stir bar was dried under vacuum using a heat gun. Anhydrous tetrahydrofuran (THF) (100 mL) was injected into the flask using a syringe. The flask was transferred to a nitrogen filled glove box. Potassium vinyldimethylsilanolate (460 mg, 4 mmol) and 18-crown-6 ether (1056 mg, 4 mmol) were then added to the THF solution. The solution was transferred from the glove box and stirred at room temperature for 20 minutes. 1,1,4,4-tetramethyl-1,4-disila-5-oxacyclopentane (6410 mg, 40 mmol) was injected into the flask using a syringe. The solution was allowed to stir for 30 seconds and 3-(dimethylchlorosilyl)propyl methacrylate (971 mg, 4.4 mmol) and anhydrous pyridine (380 mg, 4.8 mmol) were injected into the solution separately via syringe to terminate the polymerization. The solution was then washed once with deionized water (50 mL). The organic layer was precipitated three times into methanol, then the bottom layer was collected and vacuumed overnight to obtain a VS-(EDS) 90 A clear liquid of -M1 (4.1 g) was obtained.

[0126] Example 6 VS-(D3) was synthesized using the general synthetic procedure of Example 5, except that the EDS monomer was replaced with the D3 monomer. 90 -M1 crosslinker was obtained.

[0127] Example 7 AS-(EDS) 10 - Preparation of M1 (n=10) crosslinker according to the following reaction scheme: [ka]

[0128] A 50 mL flask equipped with a stirrer was dried under vacuum using a heat gun. Anhydrous toluene (20 mL) was injected into the flask using a syringe. The flask was transferred to a nitrogen filled glove box. TBD (557 mg, 4 mmol, 1 equiv.) was then added to the flask and stirred at room temperature under nitrogen for 20 min. A vacuum dried 100 mL flask was injected with 10 mL of anhydrous toluene. (Hydroxydimethylsilyl)methyl methacrylate (835 mg, 4.8 mmol, 1.2 equiv.) and 1,1,4,4-tetramethyl-1,4-disila-5-oxacyclopentane (10 g, 62.4 mmol, 10 equiv.) were added to the 100 mL flask. After TBD was completely dissolved in anhydrous toluene, the solution was transferred to the 100 mL flask using a syringe. The solution was stirred at room temperature under nitrogen for 40 min. Allyldimethylchlorosilane (700 mg, 5.2 mmol, 1.3 equiv.) and anhydrous pyridine (633 mg, 8.0 mmol, 2.0 equiv.) were separately injected into the solution using a syringe. The solution was stirred for 30 min. The solution was concentrated on a rotovap and precipitated three times in methanol (50 mL). The bottom organic layer was collected and dried in vacuum overnight to give AS-EDS-M1 (4.76 g) a viscous transparent liquid.

[0129] Example 8 VS-(D3) 10 - Preparation of M1 (X = O, Y = CH3, n = 10, m = 1) crosslinker according to the following reaction scheme: [ka]

[0130] A 25 mL flask equipped with a stirrer was dried under vacuum using a heat gun. Anhydrous toluene (15 mL) was injected into the flask using a syringe. The flask was transferred to a nitrogen filled glove box. TBD (696 mg, 5 mmol, 1 equiv.) was then added to the flask and stirred at room temperature under nitrogen for 20 minutes. A vacuum dried 50 mL flask was injected with 10 mL of anhydrous toluene. (Hydroxydimethylsilyl)methyl methacrylate (1044 mg, 6.0 mmol, 1.2 equiv.) and hexamethylcyclotrisiloxane (11.1 g, 50 mmol, 10 equiv.) were then added to the 50 mL flask. After TBD was completely dissolved in anhydrous toluene, the solution was transferred to the 50 mL flask using a syringe. The solution was stirred at room temperature under nitrogen for 60 minutes. Vinyldimethylchlorosilane (784 mg, 6.5 mmol, 1.3 equiv) and anhydrous pyridine (791 mg, 1.0 mmol, 2.0 equiv) were separately injected into the solution using a syringe. The solution was stirred for 30 min. The solution was concentrated on a rotovap and precipitated once in acetonitrile (50 mL) and twice in methanol (50 mL). The bottom organic layer was collected and dried in vacuum overnight to give VS-(D3). 10 A viscous transparent liquid of -M1 (10.2 g) was obtained.

[0131] Example 9 AS-(D3) 10 - Preparation of M1 (X = O, Y = CH3, n = 10, m = 1) crosslinker according to the following reaction scheme: [ka]

[0132] A 25 mL flask equipped with a stirrer was dried under vacuum using a heat gun. Anhydrous toluene (15 mL) was injected into the flask using a syringe. The flask was transferred to a nitrogen filled glove box. TBD (696 mg, 5 mmol, 1 equiv.) was then added to the flask and stirred at room temperature under nitrogen for 20 minutes. A vacuum dried 50 mL flask was injected with 10 mL of anhydrous toluene. (Hydroxydimethylsilyl)methyl methacrylate (1044 mg, 6.0 mmol, 1.2 equiv.) and hexamethylcyclotrisiloxane (11.1 g, 50 mmol, 10 equiv.) were then added to the 50 mL flask. After TBD was completely dissolved in anhydrous toluene, the solution was transferred to the 50 mL flask using a syringe. The solution was stirred at room temperature under nitrogen for 60 minutes. Allyldimethylchlorosilane (784 mg, 6.5 mmol, 1.3 equiv.) and anhydrous pyridine (791 mg, 1.0 mmol, 2.0 equiv.) were separately injected into the solution using a syringe. The solution was stirred for 30 min. The solution was concentrated on a rotovap and precipitated once in acetonitrile (50 mL) and twice in methanol (50 mL). The bottom organic layer was collected and dried in vacuum overnight to give VS-D3-M1 (10.2 g) a viscous clear liquid.

[0133] Examples 10 to 20 A monomer mixture was made by mixing the following components listed in Table 1 in the amounts by weight: [Table 1]

[0134] The resulting monomer mixture was cast into a contact lens by introducing the monomer mixture into a polypropylene mold assembly. The mold assembly and monomer mixture were then UV cured for about 0.5 hours to form a contact lens. The resulting contact lens was removed from the mold assembly and extracted once in 50 / 50 IPA / water for 10 minutes, once in IPA for 30 minutes, once in 50 / 50 IPA / water for 10 minutes, twice in 100% water for 10 minutes, and placed in borated buffered saline (BBS) before being autoclaved.

[0135] Examples 21 to 23 A monomer mixture was made by mixing the following components in the amounts by weight listed in Table 2. [Table 2]

[0136] The resulting monomer mixture was cast into a contact lens by introducing the monomer mixture into a polypropylene mold assembly. The mold assembly and monomer mixture were then UV cured for about -0.5 hours to form a contact lens. The resulting contact lens was removed from the mold assembly and extracted once in 50 / 50 IPA / water for 10 minutes, once in IPA for 30 minutes, once in 50 / 50 IPA / water for 10 minutes, twice in 100% water for 10 minutes, and placed in borated buffered saline (BBS) before being autoclaved.

[0137] Examples 24 to 29 A monomer mixture was made by mixing the following components in the amounts by weight listed in Table 3. [Table 3]

[0138] The resulting monomer mixture was cast into a contact lens by introducing the monomer mixture into a polypropylene mold assembly. The mold assembly and monomer mixture were then heat cured for about 3.0 hours to form a contact lens. The resulting contact lens was demolded from the mold assembly and extracted once in 50 / 50 IPA / water, once in 100% IPA, once in 50 / 50 IPA / water, twice in 100% water for 10 minutes each, and placed in borated buffered saline (BBS) before being autoclaved.

[0139] Examples 30 to 32 and Comparative Example A A monomer mixture was made by mixing the following components in the amounts by weight listed in Table 4. [Table 4]

[0140] The resulting monomer mixture was cast into a contact lens by introducing the monomer mixture into a polypropylene mold assembly. The mold assembly and monomer mixture were then heat cured for about 3.0 hours to form a contact lens. The resulting contact lens was demolded from the mold assembly and extracted once in 50 / 50 IPA / water, once in 100% IPA, once in 50 / 50 IPA / water, twice in 100% water for 10 minutes each, and placed in borated buffered saline (BBS) before being autoclaved.

[0141] Test results for the contact lenses made from Examples 30-32 and Comparative Example A are set forth in Table 5 below. [Table 5]

[0142] For the sake of brevity, various features disclosed herein are described in the context of a single embodiment, but may be provided separately or in any suitable subcombination.All combinations of the embodiments are specifically encompassed by the exemplary embodiments disclosed herein, as if each and every combination were individually and expressly disclosed herein.In addition, all subcombinations listed in the embodiments that describe such variations are also specifically encompassed by the formulation, and are disclosed herein, as if each and every combination were individually and expressly disclosed herein.

[0143] It will be understood that various modifications can be made to the embodiments disclosed herein. Thus, the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the present invention are for illustrative purposes only. Those skilled in the art can implement other configurations and methods without departing from the scope and spirit of the present invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the features and advantages added herein.

Claims

1. 1. A multifunctional crosslinker comprising one or more repeat units of a siloxanyl group or a silyl-alkyl-siloxanyl group and at least two ethylenically unsaturated reactive end groups, wherein one of the at least two ethylenically unsaturated reactive end groups is a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group and the other of the at least two ethylenically unsaturated reactive end groups is an allyl-containing reactive end group or a vinyl-containing reactive end group.

2. 2. The multifunctional crosslinker of claim 1, comprising from 3 to about 300 repeat units of said siloxanyl group.

3. The one or more repeat units include a siloxanyl group represented by the structure: 【Chemistry 1】 In the formula, R １ and R ２ are independently hydrogen, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl group, C ３ ~C １２ Heterocycloalkyl group, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ 2. The multifunctional crosslinker of claim 1, wherein y is an aromatic group and y is from 3 to about 300.

4. 4. The multifunctional crosslinker of claim 3, wherein the one or more repeat units contain siloxanyl groups derived from a stepwise anionic polymerization reaction involving 1,1,4,4-tetramethyl-1,4-disila-5-oxacyclopentane.

5. 2. The multifunctional crosslinker of claim 1, comprising from 1 to about 100 repeat units of said silyl-alkyl-siloxanyl group.

6. 6. The multifunctional crosslinker of claim 5, wherein the alkyl group of the silyl-alkyl-siloxanyl group has from 2 to about 4 carbon atoms.

7. The one or more repeat units include a silyl-alkyl-siloxanyl group represented by the structure: 【Chemistry 2】 In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are independently hydrogen, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl group, C ３ ~C １２ Heterocycloalkyl group, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ 2. The multifunctional crosslinker of claim 1, wherein a is an aromatic group, a is from 2 to 4, and x is from 1 to about 100.

8. 8. The multifunctional crosslinker of claim 7, wherein the one or more repeat units contain silyl-alkyl-siloxanyl groups derived from a stepwise anionic polymerization reaction involving hexamethylcyclotrisiloxane.

9. The multifunctional crosslinker of any one of claims 1 to 8, wherein the at least two ethylenically unsaturated reactive end groups comprise a (meth)acrylate-containing reactive end group and an allyl-containing reactive end group.

10. The multifunctional crosslinker of any one of claims 1 to 8, wherein the at least two ethylenically unsaturated reactive end groups comprise an acrylamide-containing reactive end group and an allyl-containing reactive end group.

11. The multifunctional crosslinker of any one of claims 1 to 8, wherein the at least two ethylenically unsaturated reactive end groups comprise a (meth)acrylate-containing reactive end group and a vinyl-containing reactive end group.

12. The multifunctional crosslinker of any one of claims 1 to 8, wherein the at least two ethylenically unsaturated reactive end groups comprise an acrylamide-containing reactive end group and a vinyl-containing reactive end group.

13. 1. An ophthalmic device comprising: (a) one or more multifunctional crosslinkers comprising one or more repeat units of a siloxanyl group or a silyl-alkyl-siloxanyl group and at least two ethylenically unsaturated reactive end groups, one of the at least two ethylenically unsaturated reactive end groups being a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group, and the other of the at least two ethylenically unsaturated reactive end groups being an allyl-containing reactive end group or a vinyl-containing reactive end group; (b) one or more first ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with the (meth)acrylate-containing reactive end group or the acrylamide-containing reactive end group of the multifunctional crosslinker; (c) one or more second ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the allyl-containing reactive end group or the vinyl-containing reactive end group of the multifunctional crosslinker.

14. The ophthalmic device of claim 13, wherein the one or more multifunctional crosslinkers comprise from 3 to about 300 repeat units of the siloxanyl group.

15. The one or more multifunctional crosslinkers comprise one or more repeat units of the siloxanyl group represented by the structure: 【Chemistry 3】 In the formula, R １ and R ２ are independently hydrogen, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl group, C ３ ~C １２ Heterocycloalkyl group, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ The ophthalmic device of claim 13, wherein y is an aromatic group and y is from 3 to about 300.

16. 14. The ophthalmic device of claim 13, wherein the one or more multifunctional crosslinkers comprise 1 to about 100 repeat units of the silyl-alkyl-siloxanyl group, the alkyl group of the silyl-alkyl-siloxanyl group having 2 to about 4 carbon atoms.

17. The one or more multifunctional crosslinkers comprise one or more repeat units of the silyl-alkyl-siloxanyl group represented by the structure: 【Chemistry 4】 In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are independently hydrogen, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl group, C ３ ~C １２ Heterocycloalkyl group, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ The ophthalmic device of claim 13, wherein a is an aromatic group, a is 2 to 4, and x is 1 to about 100.

18. The ophthalmic device of any one of claims 13 to 17, wherein the one or more multifunctional crosslinkers comprise (meth)acrylate-containing reactive end groups and allyl-containing reactive end groups.

19. The ophthalmic device of any one of claims 13 to 17, wherein the one or more multifunctional crosslinkers comprise acrylamide-containing reactive end groups and allyl-containing reactive end groups.

20. The ophthalmic device of any one of claims 13 to 17, wherein the one or more multifunctional crosslinkers comprise (meth)acrylate-containing reactive end groups and vinyl-containing reactive end groups.

21. The ophthalmic device of any one of claims 13 to 17, wherein the one or more multifunctional crosslinkers comprise acrylamide-containing reactive end groups and vinyl-containing reactive end groups.

22. The ophthalmic device of any one of claims 13 to 21, wherein the one or more first ophthalmic device-forming comonomers comprise one or more silicone-containing comonomers.

23. The one or more silicone-containing comonomers are represented by the structure of Formula I: 【Chemistry 5】 where V is an ethylenically unsaturated polymerizable group, L is a linker group or a bond, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , and R ９ are independently H, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl groups, heterocycloalkyl groups, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ is an aromatic group, R １０ and R １１ are independently H or C １ ~C １２ is an alkyl group, R １０ and R １１ wherein at least one of is hydrogen, y is 2 to 7, and n is 1 to 100), a silicone-containing comonomer represented by the structure of Formula II: 【Chemistry 6】 (In the formula, R １２ is H or methyl, and X is O or NR １６ and R １６ is H or C optionally substituted with one or more hydroxyl groups; １ ~C ４ alkyl group; R １３ is a divalent alkyl group, optionally functionalized with a group selected from the group consisting of ether groups, hydroxyl groups, carbamate groups, and combinations thereof; each R １４ are independently a phenyl group or a C optionally substituted with a fluorine, a hydroxyl group, or an ether group; １ ~C ４ is an alkyl group, R １５ is C １ ~C ４ and a is an alkyl group and a is 2 to 50), a polysiloxane prepolymer represented by the structure of Formula III: 【Chemistry 7】 wherein each V is independently a reactive functional end group; R １７ ~R ２２ are independently linear or branched, substituted or unsubstituted C １ ~C ３０ Alkyl group, substituted or unsubstituted C ３ ~C ３０ Cycloalkyl group, substituted or unsubstituted C ４ ~C ３０ Cycloalkylalkyl group, substituted or unsubstituted C ３ ~C ３０ Cycloalkenyl group, substituted or unsubstituted C ６ ~C ３０ Aryl groups, and substituted or unsubstituted C ７ ~C ３０ and L is, independently, a linking group), a silicone-containing comonomer represented by the structure of Formula IV: 【Chemistry 8】 (Wherein, X is —O— or —NR １９ - represents R １９ is hydrogen or C １ ~C ４ is an alkyl group, and each R １７ each independently represents hydrogen or methyl; １８ is independently １ ~C ６ represents an alkyl group, a phenyl group, or a group represented by 【Chemistry 9】 Each R １８′ is independently １ ~C ６ represents an alkyl, alkyl, or phenyl radical, and h is 1 to 10), and a silicone-containing comonomer represented by the structure of Formula V: 【Chemistry 10】 (Wherein, X is —NR １９ - represents R １９ is hydrogen or C １ ~C ４ represents an alkyl group, R １７ represents hydrogen or methyl; １８ is independently １ ~C ６ represents an alkyl group, a phenyl group, or a group represented by 【Chemistry 11】 Each R １８′ is independently １ ~C ６ 23. The ophthalmic device of claim 22, wherein h is selected from the group consisting of: an alkyl group, an alkyl group, or a phenyl group, and h is 1 to 10.

24. The ophthalmic device of any one of claims 13 to 23, wherein the one or more second ophthalmic device-forming comonomers are hydrophilic comonomers.

25. 25. The ophthalmic device of claim 24, wherein the hydrophilic comonomer is selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinylimidazolidone, N-vinylsuccinimide, N-vinylformamide, and mixtures thereof.

26. The ophthalmic device of claim 24 , wherein the hydrophilic comonomer is an acrylamide.

27. 27. The ophthalmic device of claim 26, wherein the acrylamide is selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and mixtures thereof.

28. The monomer mixture is from about 0.1% to about 50% by weight of the one or more multifunctional crosslinkers, based on the total weight of the monomer mixture; from about 1% to about 80% by weight of the one or more first ophthalmic device-forming co-monomers, based on the total weight of the monomer mixture; The ophthalmic device of any one of claims 13 to 27, comprising from about 1% to about 80% by weight of the one or more second ophthalmic device-forming comonomers, based on the total weight of the monomer mixture.

29. 29. The ophthalmic device of any one of claims 13 to 28, which is one of a contact lens and a soft hydrogel.

30. 1. A method for making an ophthalmic device, comprising: (a) curing a monomer mixture in a mold, the monomer mixture comprising: (i) one or more multifunctional crosslinkers comprising one or more repeating units of one or more siloxanyl units or one or more silyl-alkyl-siloxanyl units and at least two ethylenically unsaturated reactive end groups, one of the at least two ethylenically unsaturated reactive end groups being a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group, and the other of the at least two ethylenically unsaturated reactive end groups being an allyl-containing reactive end group or a vinyl-containing reactive end group; (ii) one or more first ophthalmic device-forming comonomers having at least one reactive group that reacts preferentially with the (meth)acrylate-containing reactive end group or the acrylamide-containing reactive end group of the multifunctional crosslinker; and (iii) one or more second ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the allyl-containing reactive end group or the vinyl-containing reactive end group of the multifunctional crosslinker; and (b) dry releasing the ophthalmic device from the mold.

31. The monomer mixture is from about 0.1% to about 50% by weight of the one or more multifunctional crosslinkers, based on the total weight of the monomer mixture; from about 1% to about 80% by weight of the one or more first ophthalmic device-forming co-monomers, based on the total weight of the monomer mixture; and about 1% to about 80% by weight of the one or more second ophthalmic device-forming co-monomers, based on the total weight of the monomer mixture.

32. The one or more multifunctional crosslinkers comprise one or more repeat units of the siloxanyl group represented by the structure: 【Chemistry 12】 In the formula, R １ and R ２ are independently hydrogen, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl group, C ３ ~C １２ Heterocycloalkyl group, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ The method of claim 30 or 31, wherein y is an aromatic group and y is from 3 to about 300.

33. The one or more multifunctional crosslinkers comprise one or more repeat units of the silyl-alkyl-siloxanyl group represented by the structure: 【Chemistry 13】 In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are independently hydrogen, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl group, C ３ ~C １２ Heterocycloalkyl group, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ 32. The method of claim 30 or 31, wherein a is an aromatic group, a is 2 to 4, and x is 1 to about 100.

34. The method of any one of claims 30 to 33, wherein the one or more multifunctional crosslinkers comprise (meth)acrylate-containing reactive end groups and allyl-containing reactive end groups.

35. The method of any one of claims 30 to 33, wherein the one or more multifunctional crosslinkers comprise acrylamide-containing reactive end groups and allyl-containing reactive end groups.

36. The method of any one of claims 30 to 33, wherein the one or more multifunctional crosslinkers comprise (meth)acrylate-containing reactive end groups and vinyl-containing reactive end groups.

37. The method of any one of claims 30 to 33, wherein the one or more multifunctional crosslinkers comprise acrylamide-containing and vinyl-containing reactive end groups.

38. The method of any one of claims 30-37, wherein the one or more first ophthalmic device-forming comonomers are one or more silicone-containing comonomers.

39. The one or more silicone-containing comonomers are represented by the structure of Formula I: 【Chemistry 14】 where V is an ethylenically unsaturated polymerizable group, L is a linker group or a bond, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , and R ９ are independently H, C １ ~C １２ Alkyl group, haloalkyl group, C ３ ~C １２ Cycloalkyl groups, heterocycloalkyl groups, C ２ ~C １２ An alkenyl group, a haloalkenyl group, or C ６ ~C １２ is an aromatic group, R １０ and R １１ are independently H or C １ ~C １２ is an alkyl group, R １０ and R １１ wherein at least one of is hydrogen, y is 2 to 7, and n is 1 to 100), a silicone-containing comonomer represented by the structure of Formula II: 【Chemistry 15】 (In the formula, R １２ is H or methyl, and X is O or NR １６ and R １６ is H or C optionally substituted with one or more hydroxyl groups; １ ~C ４ alkyl group; R １３ is a divalent alkyl group, optionally functionalized with a group selected from the group consisting of ether groups, hydroxyl groups, carbamate groups, and combinations thereof; each R １４ are independently a phenyl group or a C optionally substituted with a fluorine, a hydroxyl group, or an ether group; １ ~C ４ is an alkyl group, R １５ is C １ ~C ４ and a is an alkyl group and a is 2 to 50), a polysiloxane prepolymer represented by the structure of Formula III: 【Chemistry 16】 wherein each V is independently a reactive functional end group; R １７ ~R ２２ are independently linear or branched, substituted or unsubstituted C １ ~C ３０ Alkyl group, substituted or unsubstituted C ３ ~C ３０ Cycloalkyl group, substituted or unsubstituted C ４ ~C ３０ Cycloalkylalkyl group, substituted or unsubstituted C ３ ~C ３０ Cycloalkenyl group, substituted or unsubstituted C ６ ~C ３０ Aryl groups, and substituted or unsubstituted C ７ ~C ３０ and L is, independently, a linking group), a silicone-containing comonomer represented by the structure of Formula IV: 【Chemistry 17】 (Wherein, X is —O— or —NR １９ - represents R １９ is hydrogen or C １ ~C ４ is an alkyl group, and each R １７ each independently represents hydrogen or methyl; １８ is independently １ ~C ６ represents an alkyl group, a phenyl group, or a group represented by 【Chemistry 18】 Each R １８′ is independently １ ~C ６ represents an alkyl, alkyl, or phenyl radical, and h is 1 to 10), and a silicone-containing comonomer represented by the structure of Formula V: 【Chemistry 19】 (Wherein, X is —NR １９ - represents R １９ is hydrogen or C １ ~C ４ represents an alkyl group, R １７ represents hydrogen or methyl; １８ is independently １ ~C ６ represents an alkyl group, a phenyl group, or a group represented by 【Chemistry 20】 Each R １８′ is independently １ ~C ６ 39. The method of claim 38, wherein h is selected from the group consisting of: an alkyl group, an alkyl group, or a phenyl group; and h is 1 to 10.

40. The method of any one of claims 30 to 39, wherein the one or more second ophthalmic device-forming comonomers are hydrophilic comonomers.

41. 41. The method of claim 40, wherein the hydrophilic comonomer is selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinylimidazolidone, N-vinylsuccinimide, N-vinylformamide, and mixtures thereof.

42. 41. The method of claim 40, wherein the acrylamide is selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and mixtures thereof.

43. The method of any one of claims 30 to 42, wherein the ophthalmic device is one of a contact lens and a soft hydrogel.

Images