Hydrophilized polydiorganosiloxane vinylic crosslinker

Abstract

This invention provides a class of hydrophilic polydiorganosiloxane ethylene crosslinking agents. Each of the hydrophilic polydiorganosiloxane ethylene crosslinking agents of this invention comprises: (1) a polydiorganosiloxane segment comprising a dimethylsiloxane unit and a hydrophilic siloxane unit, each of these hydrophilic siloxane units having a methyl substituent and an organic substituent having a phosphorylcholine moiety; and (2) an olefinic unsaturated group. This invention also provides a silicone hydrogel contact lens comprising a crosslinked polymer material comprising repeating units of at least one of these hydrophilic polydiorganosiloxane ethylene crosslinking agents. This invention further provides a method for producing a hydrophilic contact lens from a polymerizable composition comprising at least one of these hydrophilic polydiorganosiloxane ethylene crosslinking agents.

Description

[0001] This invention relates to hydrophilic polydiorganosiloxane ethylene crosslinking agents and their use in the manufacture of silicone hydrogel contact lenses. These hydrophilic polydiorganosiloxane ethylene crosslinking agents each have one or more hydrophilic siloxane units, each hydrophilic siloxane unit having a methyl substituent and an organic substituent having a phosphorylcholine moiety. Background Technology

[0002] In recent years, soft silicone hydrogel contact lenses have become increasingly popular due to their high oxygen permeability and comfort. "Soft" contact lenses conform closely to the shape of the eye, so oxygen doesn't easily bypass the lens. Soft contact lenses must allow oxygen from the surrounding air (i.e., oxygen) to reach the cornea because the cornea cannot receive oxygen supplied by the blood like other tissues. If insufficient oxygen reaches the cornea, corneal swelling occurs. Prolonged hypoxia causes unwanted blood vessel growth in the cornea. By having high oxygen permeability, silicone hydrogel contact lenses allow sufficient oxygen to permeate through the lens to the cornea with minimal adverse effects on corneal health.

[0003] One widely used lens-forming material in the manufacture of silicone hydrogel contact lenses is a polydimethylsiloxane (e.g., polydimethylsiloxane) vinyl crosslinker, which can provide high oxygen permeability to the resulting contact lens. However, polydimethylsiloxane vinyl crosslinkers can affect the mechanical properties of the resulting contact lens, such as the elastic modulus. For example, low molecular weight polydimethylsiloxane vinyl crosslinkers (<2,000 g / mol) can provide a contact lens with a relatively high elastic modulus to achieve the desired oxygen permeability. Relatively high molecular weight polydimethylsiloxane vinyl crosslinkers are typically used to achieve high oxygen permeability and low elastic modulus. However, due to their hydrophobic properties, polydimethylsiloxane vinyl crosslinkers (especially high molecular weight polydimethylsiloxane vinyl crosslinkers) are not compatible with hydrophilic components in lens formulations, including, for example, N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), N-vinyl-N-methylacetamide (VMA), or internal wetting agents. Obtaining uniform lens formulations (i.e., transparent lens formulations) using this type of polydimethylsiloxane ethylene crosslinking agent will be difficult.

[0004] Incorporating silicone into contact lens materials also has undesirable effects on the biocompatibility of contact lenses, as silicone is hydrophobic and has a strong tendency to migrate on lenses exposed to air. Therefore, silicone hydrogel contact lenses typically require surface modification processes to eliminate or minimize silicone exposure and to maintain a biocompatible surface.

[0005] Therefore, there is a need for new hydrophilic polydiorganosiloxane ethylene crosslinking agents suitable for the production of silicone hydrogel contact lenses.

[0006] Documents (including US patents 4260725, 5034461, 5346946, 5416132, 5449729, 5486579, 5512205, 5760100, 5994488, 6858218, 6867245, 7671156, 7744785, 8129442, 8163206, 850183) 3. 8513325, 8524850, 8835525, 8993651, 9187601, 10081697, 10449740, 10866344 and 10875967 disclose various lens formulations (which are solvent-containing or solvent-free formulations) containing one or more hydrophilic polysiloxane crosslinking agents that can be used to manufacture silicone hydrogel contact lenses. Summary of the Invention

[0007] In one aspect, the present invention provides a polysiloxane-ethylene crosslinking agent. The polydiorganosiloxane-ethylene crosslinking agent of the present invention comprises a polydiorganosiloxane segment and an olefinically unsaturated group, wherein the polydiorganosiloxane segment comprises a dimethylsiloxane unit and a hydrophilic siloxane unit, the hydrophilic siloxane unit having a methyl substituent and an organic substituent having a phosphorylcholine moiety.

[0008] In another aspect, the present invention provides a soft contact lens comprising a crosslinked polymer material comprising units of the polydiorganosiloxane ethylene crosslinking agent (described above) of the present invention.

[0009] The present invention provides the foregoing features and other features, and the advantages of the invention will be further understood from the following detailed description of the presently preferred embodiments, read in conjunction with the accompanying drawings. The detailed description and drawings are merely illustrative of the invention and do not limit its scope, which is defined by the appended claims and their equivalents. Detailed Implementation

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Generally, the nomenclature and laboratory procedures used herein are those well-known and commonly used in the art. Conventional methods are applied to these procedures, as those provided in the art and in various general references. When a term is provided in the singular, the inventors have also considered the plural form of that term. The nomenclature used herein and the laboratory procedures described below are those well-known and commonly used in the art.

[0011] In this application, as used herein, “about” means a number referred to as “about” that comprises the stated number plus or minus 1% to 10% of that stated number.

[0012] "Contact lenses" are structures that can be placed on or inside the wearer's eye. Contact lenses can correct, improve, or alter a user's vision, but are not required to do so.

[0013] "Silicone hydrogel contact lens" refers to a contact lens that contains silicone hydrogel material as its body material.

[0014] "Hydrogel" or "hydrogel material" refers to a cross-linked polymer material having a three-dimensional polymer network (i.e., polymer matrix) that is insoluble in water but can retain at least 10% by weight of water in its polymer matrix when fully hydrated (or in equilibrium).

[0015] "Silicone hydrogel" refers to a silicone hydrogel comprising repeating units of at least one silicone monomer and / or a silicone vinyl crosslinking agent and repeating units of at least one hydrophilic vinyl monomer. It is typically formed by copolymerization of a polymerizable composition comprising at least one silicone monomer and / or a silicone vinyl crosslinking agent and at least one hydrophilic vinyl monomer.

[0016] As used in this application, the term "non-silicone hydrogel" refers to a hydrogel that is theoretically free of silicone.

[0017] As used in this article, "hydrophilic" describes a material or part thereof that will associate with water more readily than lipids.

[0018] "Ethylene monomers" refer to compounds that have a unique olefinic unsaturated group, are soluble in solvents, and can be photochemically or thermally polymerized.

[0019] The term "soluble" in relation to a compound or material in a solvent means that the compound or material is soluble in the solvent at room temperature (i.e., at a temperature of about 21°C to about 27°C) to obtain a solution having a concentration of at least about 0.5% by weight.

[0020] The term "insoluble" in relation to compounds or materials in solvents means that the compound or material is soluble in the solvent at room temperature (as defined above) to obtain a solution with a concentration of less than 0.01% by weight.

[0021] The term "olefinic unsaturated group" is used broadly herein and is intended to cover any group containing at least one >C=C< group. Exemplary olefinic unsaturated groups include, but are not limited to, (meth)acryloyl ( and / or ), allyl, vinyl, styrene, or other C=C groups.

[0022] As used herein, “photochemical” in relation to the curing, crosslinking, or polymerization of polymerizable compositions, prepolymers, or materials means curing (e.g., crosslinking and / or polymerization) by photochemical radiation, such as UV irradiation, ionizing radiation (e.g., gamma-ray or X-ray irradiation), microwave irradiation, etc. Thermal curing or photochemical curing methods are well known to those skilled in the art.

[0023] "Acrylic monomers" refer to ethylene monomers having a single (meth)acrylyl group. Examples of acrylic monomers include (meth)acryloxy ((meth)acryloyloxy) monomers and (meth)acrylamidoyl monomers.

[0024] "(meth)acryloxy ((meth)acryloxy or (meth)acryloyloxy) monomer" refers to a monomer with a unique group. Ethylene monomers.

[0025] "(meth)acrylamide monomer" refers to a monomer with a unique group. (where R) o It is an ethylene monomer (either H or C1-C4 alkyl).

[0026] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0027] The term "(meth)acrylate" refers to methacrylates and / or acrylates.

[0028] "N-vinylamide monomer" refers to an amide compound having a vinyl group (-CH=CH2) directly attached to a nitrogen atom of the amide group.

[0029] The term "ene group" refers to a monovalent group, CH2=CH- or CH2=CCH3-, that is non-covalently attached to an oxygen or nitrogen atom or a carbonyl group.

[0030] "Ene monomer" refers to an ethylene monomer that has a unique alkenyl group.

[0031] As used herein, “hydrophilic vinyl monomer,” “hydrophilic acrylic monomer,” “hydrophilic (meth)acryloyloxy monomer,” or “hydrophilic (meth)acrylamide monomer” refers to vinyl monomers, acrylic monomers, (meth)acryloyloxy monomers, or (meth)acrylamide monomers that typically produce homopolymers that are water-soluble or capable of absorbing at least 10 percent by weight of water.

[0032] As used herein, “hydrophobic vinyl monomer,” “hydrophobic acrylic monomer,” “hydrophobic (meth)acryloyloxy monomer,” or “hydrophobic (meth)acrylamide monomer” refers to vinyl monomers, acrylic monomers, (meth)acryloyloxy monomers, or (meth)acrylamide monomers that typically produce homopolymers that are insoluble in water or can absorb less than 10% by weight of water.

[0033] As used in this application, the term "ethylene-based crosslinking agent" refers to an organic compound having at least two olefinically unsaturated groups. "Ethylene-based crosslinking agent" also refers to an ethylene-based crosslinking agent having a molecular weight of 700 Daltons or less.

[0034] Siloxanes, often described as silicones, are molecules having at least one -Si-O-Si- moiety, where each Si atom carries two organic groups as substituents.

[0035] "Silicone-containing ethylene monomers or crosslinking agents" or "siloxane-containing ethylene monomers or crosslinking agents" can be used interchangeably to refer to ethylene monomers or crosslinking agents having at least one -Si-O-Si- moiety in which each Si atom carries at least two substituents (organic groups).

[0036] "Polysiloxane segment" or "polydiorganosiloxane segment" can be used interchangeably to refer to polymer chain segments (i.e., divalent groups). Where SN is an integer of 3 or greater, and R S1 and R S2 Each of them is independently selected from the following groups: C1-C 10 Alkyl; phenyl; C1-C4-alkyl-substituted phenyl; C1-C4-alkoxy-substituted phenyl; phenyl-C1-C6-alkyl; C1-C 10 Fluoroalkyl; C1-C 10 Fluoroethers; aryl; aryl C1-C 18 Alkyl group; -alk-(OC2H4) γ1 -OR o (where alk is a C1-C6 alkylene dienoyl group, R) o It is H or C1-C4 alkyl and γ1 is an integer from 1 to 10; C2-C 40 An organic group having at least one selected from a hydroxyl (-OH), carboxyl (-COOH), or amino (-NR) group. N1 R N1 '), amino linkage -NR N1 - Amide linkage -CONR N1 - Amide-CONR N1 R N1', a functional group consisting of urethane linkage -OCONH- and C1-C4 alkoxy groups, or a straight-chain hydrophilic polymer chain, wherein R N1 and R N1 'Independently hydrogen or C1-C 15 Alkyl groups; and organic groups having a phosphorylcholine moiety.

[0037] "Polydiorganosiloxane ethylene crosslinking agent" or "polysiloxane ethylene crosslinking agent" can be used interchangeably to refer to a compound containing at least one polysiloxane segment and at least two olefinic unsaturated groups.

[0038] As used in this application, the term "phosphorylcholine moiety" refers to the zwitterionic moiety. Where n is an integer from 1 to 5, and R' and R” are independently C1-C8 alkyl or C1-C8 hydroxyalkyl, R”' is a C1-C8 alkylene divalent group, and T0 is hydrogen, hydroxyl, C1-C4 alkoxy, or covalent.

[0039] As used in this article, the term "fluid" indicates that a material is capable of flowing like a liquid.

[0040] As used in this application, the term "transparent" in relation to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture having a light transmittance of 85% or greater (preferably 90% or greater) in the range of 400 nm to 700 nm.

[0041] As used in this application, the term "polymer" means a material formed by polymerizing / crosslinking one or more monomers or macromonomers or prepolymers or combinations thereof.

[0042] "Macromonomer" or "prepolymer" refers to a compound or polymer that contains olefinic unsaturated groups and has a number-average molecular weight greater than 700 Daltons.

[0043] As used in this application, the term "molecular weight" for polymeric materials (including monomeric materials or macromonomeric materials) is exponential average molecular weight, unless otherwise specified or unless the test conditions indicate otherwise. Those skilled in the art know how to determine the molecular weight of a polymer using known methods, such as GPC (gel permeation chromatography) having one or more of the following: a refractive index detector, a small-angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscometry detector, a UV detector, and an infrared (IR) detector; or MALDI-TOF MS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometry). 1 1H NMR (proton nuclear magnetic resonance) spectroscopy, etc.

[0044] The term "monovalent group" refers to an organic group obtained by removing a hydrogen atom from an organic compound and forming a bond with another group in the organic compound. Examples include, but are not limited to, alkyl (by removing a hydrogen atom from an alkane), alkoxy (by removing a hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing a hydrogen atom from the mercapto group of an alkyl thiol), cycloalkyl (by removing a hydrogen atom from a cycloalkanes), heteroalkyl (by removing a hydrogen atom from a cycloalkanes), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing a hydrogel atom from an amine), etc.

[0045] The term "divalent group" refers to an organic group obtained by removing two hydrogen atoms from an organic compound and forming two bonds with two other groups in the organic compound. For example, an alkylene (alkylenyl) divalent group is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene (cycloalkylenyl) divalent group is obtained by removing two hydrogen atoms from a ring.

[0046] In this application, the term "substituted" in relation to alkyl or alkylene means that the alkyl or alkylene comprises at least one substituent that replaces one hydrogen atom of the alkyl or alkylene and is selected from the group consisting of: hydroxyl (-OH), carboxyl (-COOH), -NH2, mercapto (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkyl sulfide), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0047] The term "terminal olefin unsaturated group" refers to an olefin unsaturated group located at one of the two ends of the main chain (or backbone) of an organic compound, as is known to those skilled in the art.

[0048] "Blended ethylene monomers" refers to ethylene monomers that can dissolve both the hydrophilic and hydrophobic components of a polymerizable composition to form a solution.

[0049] Free radical initiators can be photoinitiators or thermal initiators. "Photoinitiators" are chemicals that initiate free radical cross-linking / polymerization reactions using light. "Thermal initiators" are chemicals that initiate free radical cross-linking / polymerization reactions using heat energy.

[0050] The term "post-curing surface treatment" for silicone hydrogel body materials or SiHy contact lenses refers to the surface treatment process performed after the SiHy lens preparation is formed into a silicone hydrogel body material or SiHy contact lens through curing (i.e., polymerization by thermal or photochemical means).

[0051] The terms “silicone hydrogel lens preparation” or “SiHy lens preparation” can be used interchangeably to refer to a polymerizable composition comprising all the necessary polymerizable components as well known to those skilled in the art for the production of silicone hydrogel (SiHy) contact lenses or SiHy lens body materials.

[0052] In general, the present invention relates to a class of hydrophilic polydiorganosiloxane ethylene crosslinking agents, each comprising: (1) a polydiorganosiloxane segment comprising a dimethylsiloxane unit and a hydrophilic siloxane unit having a methyl substituent and an organic substituent having a phosphorylcholine moiety; and (2) an olefinic unsaturated group.

[0053] In the manufacture of silicone hydrogel contact lenses, there are some potential unique features related to the use of the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention.

[0054] First, the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention is more compatible with other polymerizable components in typical polymerizable compositions (i.e., lens formulations) used in the manufacture of contact lenses because the phosphorylcholine moiety of the hydrophilic ion is incorporated in the polydiorganosiloxane ethylene crosslinking agent as one of the two substituents of each hydrophilic siloxane unit. It is suitable for preparing a variety of solvent-containing or solvent-free lens formulations.

[0055] Secondly, because the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention still contains dimethylsiloxane units, it can provide a relatively high oxygen permeability to the resulting contact lens, just like other polydimethylsiloxane ethylene crosslinking agents currently used in the manufacture of silicone hydrogel contact lenses. It is believed that, in order to achieve a high oxygen permeability, the polydiorganosiloxane should have at least five consecutive dimethylsiloxane units. By controlling the ratio of hydrophilic siloxane units to dimethylsiloxane units in the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention to a sufficiently low level, it can be ensured that the resulting polydiorganosiloxane ethylene crosslinking agent can have sufficient siloxane segments consisting of more than five consecutive dimethylsiloxane units. Such a polydiorganosiloxane ethylene crosslinking agent can be used to effectively provide a relatively high oxygen permeability per siloxane unit without adversely affecting its compatibility with other polymerizable components.

[0056] Third, the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention can be used to produce silicone hydrogel contact lenses with improved surface properties. Because the phosphorylcholine moiety is part of the polydiorganosiloxane chain segment, when silicone migrates to the lens surface, these phosphorylcholine moiety portions will migrate to the surface of the resulting silicone hydrogel contact lens manufactured from a lens formulation containing the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention. Therefore, the resulting silicone hydrogel contact lens can have phosphorylcholine moiety enriched on the lens surface.

[0057] Phosphorylcholine is commonly used in medical devices to improve biocompatibility, reduce protein adsorption, and decrease inflammatory responses. Phospholipid-containing surfaces have been shown to have antifouling properties (see Goda, T.; Ishihara, K.; Expert Review of Medical Devices, 2006, 3(2), 167-174). In contact lenses, phosphorylcholine helps maintain hydration while preventing lipid and protein deposition. Based on these observations, monomers or polymers containing phosphorylcholine groups have been added to contact lens formulations (see, for example, Liu, Y. Polymerizable contact lens formulations and contact lenses obtained therefrom. U.S. Patent 2009 / 0182067A1, July 16, 2009), lubricating eye drops (see, for example, Sakurai, S.; Miyamoto, K.; Shimamura, Y.; Takahashi, M.; Matsuoka, Y.; Yamamoto, N. Eye drops. WO / 2016 / 140242, September 9, 2016), and contact lens surfaces (see, for example, Takahashi, M.; Sato, K.; Sakurai, T.; Nakajima, M.; Matsuoka, Yamamoto, N. Contact lens having phosphorylcholine group-containing hydrophilic polymer on surface). The contact lenses thereof [contact lenses having hydrophilic polymers containing phosphorylcholine groups on their surface]. JP 2017146334, August 24, 2017), and packaged in saline solution (Sakurai, T.; Sato, K.; Takahashi, M.; Nakajima, M.; Matsuoka, Y.; Shimamura, Y.; Miyamoto, K.; Yamamoto, N. Solutions for soft contact lenses. JP 2017151437, August 31, 2017) to improve the performance of the contact lenses on the eye.

[0058] Therefore, the resulting silicone hydrogel contact lenses can be more biocompatible and resistant to lipid deposition.

[0059] In one aspect, the present invention provides a hydrophilic polydiorganosiloxane ethylene crosslinking agent. The hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention comprises: (1) a polydiorganosiloxane segment comprising a dimethylsiloxane unit and at least one hydrophilic siloxane unit having a methyl substituent and an organic substituent having a phosphorylcholine moiety, and (2) an olefinic unsaturated group (preferably (meth)acryloyl).

[0060] In a preferred embodiment, the polydiorganosiloxane segment comprises 6 to 500 (preferably 10 to 450, more preferably 15 to 400, and even more preferably 20 to 350) dimethylsiloxane units and 3 to 80 (preferably 5 to 70, more preferably 7 to 60, and even more preferably 9 to 50) hydrophilic siloxane units.

[0061] In a preferred embodiment, the molar ratio of the hydrophilic siloxane unit to the dimethyl siloxane unit is from about 0.002 to about 0.50 (preferably from about 0.002 to about 0.20, more preferably from about 0.004 to about 0.1, and even more preferably from about 0.004 to about 0.05).

[0062] In another preferred embodiment, the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention may have a number average molecular weight of at least 1,000 Daltons (preferably from 1,500 Daltons to 80,000 Daltons, more preferably from 2,000 to 50,000 Daltons, and even more preferably from 2,500 to 25,000 Daltons).

[0063] According to the present invention, the hydrophilic polydiorganosiloxane ethylene crosslinking agent is preferably defined by formula (1) or (2).

[0064]

[0065] in:

[0066] υ1 is an integer from 6 to 500 (preferably from 10 to 450, more preferably from 15 to 400, and even more preferably from 20 to 350);

[0067] ω1 is an integer from 3 to 80 (preferably from 5 to 70, more preferably from 7 to 60, and even more preferably from 9 to 50);

[0068] γ1 is an integer from 1 to 78 (preferably from 3 to 68, more preferably from 5 to 58, and even more preferably from 7 to 48);

[0069] E1 is Monovalent groups;

[0070] E2 is Monovalent groups;

[0071] R0 is either hydrogen or methyl;

[0072] a1 is zero or 1;

[0073] X0 is either O or NR N1 ;

[0074] R N1 It is hydrogen or C1-C6 alkyl;

[0075] L0 is a C2-C8 alkylene divalent group, or -L0′-X1-L0″-. divalent groups;

[0076] L0' is a C2-C8 alkylene divalent group;

[0077] "L0" is a C3-C8 alkylene divalent group;

[0078] X1 is -O-, -NR N1 -、-NHCOO-、-OCONH-、-CONR N1 -or-NR N1 CO-;

[0079] q1 is an integer from 1 to 20;

[0080] R PC yes Monovalent groups;

[0081] L e It is -CH2-CHR0-R 1- -C3H6-O-R2- divalent groups;

[0082] R1 is a C1-C chain, whether straight or branched. 10 alkylene divalent groups;

[0083] R2 is a straight or branched C3-C. 10 alkylene divalent groups;

[0084] R3 is a C1-C4 alkylene divalent group that is either directly bonded, straight-chain, or branched;

[0085] n is an integer from 1 to 5;

[0086] R' and R” are independently C1-C8 alkyl or C1-C8 hydroxyalkyl;

[0087] R”' is a C1-C8 alkylene divalent group;

[0088] T1 is hydrogen, hydroxyl, or C1-C4 alkoxy; and

[0089] T2 is a C1-C8 alkyl, C1-C8 hydroxyalkyl, R4-O-R5-, or -R PC -T1;

[0090] R4 is a C1-C4 alkyl group; and

[0091] R5 is a C2-C8 alkylene divalent group.

[0092] In a preferred embodiment, in equation (1), a1 is zero and then E1 is Monovalent groups.

[0093] In another preferred embodiment, ω1 / υ1 is from about 0.002 to about 0.50 (preferably from about 0.002 to about 0.20, more preferably from about 0.004 to about 0.1, and even more preferably from about 0.004 to about 0.05).

[0094] Hydrophilic polydiorganosiloxane ethylene crosslinking agents having formula (1) can be prepared by a three-step method.

[0095] In the first step, a polydiorganosiloxane having the hydrosiloxane of formula (3) is reacted with a hydroxyl-containing olefin monomer in a platinum-catalyzed hydrosilylation reaction as known to those skilled in the art, to form a polydiorganosiloxane ethylene crosslinking agent having side-group reactive functional groups as represented by formula (4).

[0096]

[0097] Where E1, υ1, ω1 and L e It is as defined above for equation (1).

[0098] Polydiorganosiloxanes having the hydrogenated siloxane of formula (3) can be prepared according to any method known to those skilled in the art.

[0099] As an exemplary example, a polydiorganosiloxane having a hydrogenated siloxane of formula (3) can be prepared by polymerization of a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of a 1,3-bis(E1 group)-terminated tetramethyldisiloxane (e.g., 1,3-bis[3-(meth)acryloyloxypropyl]tetramethyldisiloxane, 1,3-bis[3-(meth)acrylamidopropyl]tetramethyldisiloxane, etc.) as chain-end blocks and in the presence of a catalyst. The desired υ1 / ω1 value can be obtained by controlling the molar ratio of D4 to H4. It should be understood that 1,3-bis(E1 group)-terminated tetramethyldisiloxanes can be prepared from 1,3-bis(hydroxyalkyl)tetramethyldisiloxanes (e.g., 1,3-bis(hydroxypropyl)tetramethyldisiloxane) or 1,3-bis(aminoalkyl)tetramethyldisiloxanes (e.g., 1,3-bis(aminopropyl)tetramethyldisiloxane).

[0100] Any olefin monomer can be used in the preparation of polydiorganosiloxane ethylene crosslinking agents having formula (4), provided that the olefin monomer contains a single hydroxyl group. Various olefin monomers having a single hydroxyl group can be obtained from commercial suppliers or prepared according to known methods.

[0101] Commercially available examples of hydroxyl-containing alkenyl monomers include, but are not limited to, allyl alcohol, 2-methyl-2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, 1-penten-3-ol, 4-penten-1-ol, 4-penten-2-ol, 1-hexen-3-ol, 5-hexen-1-ol, 5-hexen-2-ol, 3-methyl-1-hexen-3-ol, 5-methyl-1-hexen-3-ol, 1-hepten-3-ol, and allyloxyethyl. Alcohols, di(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, poly(propylene glycol) monoallyl ether, allyloxypropanol, 1-allyloxy-2-propanol, 4-allyloxy-1-butanol, 1-vinylcyclohexanol, 2-vinylcyclohexanol, 4-vinylcyclohexanol, 1-allylcyclohexanol, 2-allylcyclohexanol, 4-allylcyclohexanol, 4-vinylphenol, (4-vinylphenyl)methanol, (4-vinylphenyl)ethanol, 3-(4-vinylphenyl)-1-propanol, 1-(4-vinylphenyl)-2-methyl-2-propanol, etc.

[0102] In the second step, a polydiorganosiloxane ethylene crosslinking agent having formula (4) is reacted with ethylenephosphorochloride (i.e., 2-chloro-2-oxo-1,3,2-dioxophosphazenecyclopentane) in the presence of a base (e.g., triethylamine) to remove the ethylene phosphate groups. (i.e., 2-oxo-1,3,2-dioxophosphoryloxy) is attached to each side group L of a polydiorganosiloxane ethylene crosslinker having formula (4). e superior.

[0103] Alternatively, a polydiorganosiloxane ethylene crosslinking agent having formula (4) can be reacted with bromoalkyl phosphoryl chloride (which can be reacted with bromoethanol (HO-(CH2)). n The reaction (Br) is obtained by reacting in the presence of a base (e.g., triethylamine), followed by acid hydrolysis to obtain one or more bromoalkyl phosphate groups. Each side group L of the polydiorganosiloxane ethylene crosslinking agent having formula (4) is attached to e superior.

[0104] In the third step, the obtained polydiorganosiloxane ethylene crosslinking agent containing side ethylene phosphate group or bromoalkyl phosphate group can be further treated with tertiary amine NR1'R2'R3' to convert it into phosphorylcholine group, that is, to form a hydrophilic polydiorganosiloxane ethylene crosslinking agent having formula (1).

[0105] Similarly, hydrophilic polydiorganosiloxane ethylene crosslinking agents having formula (2) can be prepared in a three-step process.

[0106] In the first step, a polydiorganosiloxane having the hydrosiloxane of formula (5) is reacted with a hydroxyl-containing olefin monomer in a platinum-catalyzed hydrosilylation reaction as known to those skilled in the art, to form a polydiorganosiloxane ethylene crosslinking agent having side-group reactive functional groups as represented by formula (5).

[0107]

[0108] Where E1, υ1, ω1 and L e It is as defined above for equation (2).

[0109] Polydiorganosiloxanes having the hydrogenated siloxane of formula (5) can be prepared according to any method known to those skilled in the art.

[0110] As an exemplary example, a polydiorganosiloxane having a hydrogenated siloxane of formula (5) can be prepared by polymerization of a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of a 1,3-bis(T2 group)-terminated tetramethyldisiloxane (e.g., 1,3-bis(3-hydroxyethoxypropyl)tetramethyldisiloxane, etc.) as a chain-end block and in the presence of a catalyst. The desired υ1 / ω1 value can be obtained by controlling the molar ratio of D4 to H4.

[0111] In the second step, a polydiorganosiloxane ethylene crosslinking agent having formula (6) is reacted with ethylene phosphoryl chloride (i.e., 2-chloro-2-oxo-1,3,2-dioxophosphazenecyclopentane) in the presence of a base (e.g., triethylamine) to remove the ethylene phosphate groups. (i.e., 2-oxo-1,3,2-dioxophosphoryloxy) is attached to each side group L of a polydiorganosiloxane ethylene crosslinker having formula (6). e superior.

[0112] Alternatively, a polydiorganosiloxane ethylene crosslinking agent having formula (6) can be reacted with a bromoalkyl phosphoryl chloride (which can be reacted with a bromoalcohol (HO-(CH2)). n The reaction (Br) is obtained by reacting in the presence of a base (e.g., triethylamine), followed by acid hydrolysis to obtain one or more bromoalkyl phosphate groups. Each side group L of the polydiorganosiloxane ethylene crosslinking agent having formula (6) is attached to e superior.

[0113] In the third step, the obtained polydiorganosiloxane ethylene crosslinking agent containing side ethylene phosphate group or bromoalkyl phosphate group can be further treated with tertiary amine NR1'R2'R3' to convert it into phosphorylcholine group, that is, to form a hydrophilic polydiorganosiloxane ethylene crosslinking agent having formula (2).

[0114] The hydrophilic polydiorganosiloxane ethylene crosslinking agents of the present invention (such as those defined above as formula (1) or (2)) can find particular use in the preparation of polymers, preferably silicone hydrogel polymer materials, which is another aspect of the present invention. Those skilled in the art know how to prepare polymers or silicone hydrogel polymer materials from polymerizable compositions according to any known polymerization mechanism.

[0115] In another aspect, the present invention provides a silicone hydrogel contact lens comprising a crosslinked polymer material comprising repeating units of the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention (as described above).

[0116] In a preferred embodiment, when fully hydrated, the silicone hydrogel contact lens of the present invention has an oxygen permeability (Dk) of at least about 40 bar (preferably at least about 60 bar, more preferably at least about 70 bar, and even more preferably at least about 80 bar), a water content of from about 15% to about 70% by weight (preferably from about 20% to about 70% by weight, more preferably from about 25% to about 65% by weight, and even more preferably from about 30% to about 60% by weight), and an elastic modulus of from about 0.20 MPa to about 1.8 MPa (preferably from about 0.25 MPa to about 1.5 MPa, more preferably from about 0.3 MPa to about 1.2 MPa, and even more preferably from about 0.4 MPa to about 1.0 MPa).

[0117] Those skilled in the art are familiar with how to measure the oxygen permeability, oxygen transmission rate, water content, and elastic modulus of silicone hydrogel contact lenses. All manufacturers have reported these lens properties for their silicone hydrogel contact lens products.

[0118] The silicone hydrogel contact lens of the present invention further comprises at least one unit of a polymerizable silicone component and at least one unit of a hydrophilic ethylene monomer.

[0119] According to the present invention, the silicone-containing polymerizable component other than the hydrophilic polydiorganosiloxane ethylene crosslinking agent of the present invention may be a silicone-containing ethylene monomer, a polysiloxane ethylene crosslinking agent, or a combination thereof.

[0120] According to the present invention, the silicone-containing vinyl monomer can be any silicone-containing vinyl monomer known to those skilled in the art. Preferred examples of silicone-containing vinyl monomers include, but are not limited to, vinyl monomers each having a bis(trialkylsiloxy)alkylsilyl or tri(trialkylsiloxy)silyl group, polysiloxane vinyl monomers, 3-methacryloyloxypropylpentamethyldisiloxane, tert-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0121] Preferred polysiloxane vinyl monomers, including those having formula (M1), are described later in this application and are available from commercial suppliers (e.g., Shin-Etsu, Gelest, etc.); prepared according to the procedures described in patents, such as U.S. Patent Nos. 5,070,215, 6,166,236, 6,867,245, 8,415,405, 8,475,529, 8,614,261, and 9,217,813; by making (meth)acrylate hydroxyalkyl esters or (methyl)methacrylate esters... It can be prepared by reacting acrylamide or (meth)acryloyloxy polyethylene glycol with a mono-epoxypropoxypropyl-terminated polydimethylsiloxane; by reacting (meth)acrylate with a mono-methanol-terminated polydimethylsiloxane, a mono-aminopropyl-terminated polydimethylsiloxane, or a mono-ethylaminopropyl-terminated polydimethylsiloxane; or by reacting (meth)acrylate isocyanate ethyl with a mono-methanol-terminated polydimethylsiloxane according to a coupling reaction well known to those skilled in the art.

[0122] Preferred silicone-containing vinyl monomers (including those having formula (M2)) each having a bis(trialkylsilyloxy)alkylsilyl or tri(trialkylsiloxy)silyl group are described later in this application and are available from commercial suppliers (e.g., Shin-Etsu Corporation, Gallest Corporation, etc.) or can be prepared according to the procedures described in U.S. Patent Nos. 5070215, 6166236, 7214809, 8475529, 8658748, 9097840, 9103965, and 9475827.

[0123] Any suitable polysiloxane-vinyl crosslinking agent can be used in this invention. Preferred examples of polysiloxane-vinyl crosslinking agents are di-(meth)acryloyl-terminated polydimethylsiloxanes; divinyl carbonate-terminated polydimethylsiloxanes; divinyl carbamate-terminated polydimethylsiloxanes; N,N,N',N'-tetratetra(3-methacryloyloxy-2-hydroxypropyl)-α,ω-bis-3-aminopropyl-polydimethylsiloxanes; selected from US The polysiloxane-containing macromonomers comprising the group consisting of macromonomers A, B, C, and D as described in U.S. Patent Nos. 4,760,100; and the polysiloxane-containing macromonomers disclosed in U.S. Patent Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, 4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538, 4,703,097, 4,833,218, 4,4,760,100. The polysiloxane-containing macromonomers in 837289, 4954586, 4954587, 5010141, 5034461, 5070170, 5079319, 5039761, 5346946, 5358995, 5387632, 5416132, 5451617, 5486579, 5962548, 5981675, 6039913, and 6762264; and the polysiloxane-containing macromonomers disclosed in U.S. Patent Nos. 4259467, 4260725, and 4261875.

[0124] A preferred class of polysiloxane ethylene crosslinking agents is di(meth)acryloyloxy-terminated polysiloxane ethylene crosslinking agent, each having a dimethylsiloxane unit and a hydrophilic siloxane unit (each having a methyl substituent and a monovalent C4-C having 2 to 6 hydroxyl groups). 40 Organic substituents), more preferably polysiloxane ethylene crosslinking agents having formula (I) are described later in this application and can be prepared according to the procedure disclosed in U.S. Patent No. 10081697.

[0125] Another preferred class of polysiloxane ethylene crosslinking agents are the following ethylene crosslinking agents, each comprising a unique polydiorganosiloxane segment and two terminal (meth)acryloyl groups, which are available from commercial suppliers; prepared by reacting (meth)acryloyl chloride glycidyl acrylate with di-amino-terminated polydimethylsiloxane or di-hydroxy-terminated polydimethylsiloxane; prepared by reacting ethyl isocyanate of (meth)acrylate with di-hydroxy-terminated polydimethylsiloxane (prepared by reacting an amino-containing acrylic monomer with a di-carboxyl-terminated polydimethylsiloxane) in the presence of a coupling agent (carbodiimide); prepared by reacting a carboxyl-containing acrylic monomer with a di-amino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or prepared by reacting a hydroxyl-containing acrylic monomer with a di-hydroxy-terminated polydisiloxane in the presence of a diisocyanate or a di-epoxy coupling agent.

[0126] Other preferred types of polysiloxane ethylene crosslinking agents are chain-extended polysiloxane ethylene crosslinking agents, each having at least two polydiorganosiloxane segments linked by a linker between each pair of polydiorganosiloxane segments and two terminal olefinic unsaturated groups, which can be prepared according to the procedures described in U.S. Patent Nos. 5034461, 5416132, 5449729, 5760100, 7423074, 8529057, 8835525, 8993651, 10301451, and 10465047.

[0127] Any hydrophilic vinyl monomer can be used in this invention. Preferred examples of hydrophilic vinyl monomers are alkyl (meth)acrylamides (as described later in this application), hydroxyl-containing acrylic monomers (as described below), amino-containing acrylic monomers (as described later in this application), carboxyl-containing acrylic monomers (as described later in this application), N-vinylamide monomers (as described later in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group linked to a pyrrolidone ring at the 3 or 5 position) (as described later in this application), acrylic monomers having a C1-C4 alkoxyethoxy group (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), phosphorylcholine-containing vinyl monomers (as described later in this application), N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-propane (VINAL), N-carboxyvinyl-α-propane, and combinations thereof.

[0128] The silicone hydrogel contact lens of the present invention may further comprise at least one hydrophobic vinyl monomer, at least one non-silicone vinyl crosslinking agent, or a combination thereof.

[0129] According to the present invention, any hydrophobic vinyl monomer can be used. Preferred examples of hydrophobic vinyl monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, methacrylonitrile, 1-butene, butadiene, vinyltoluene, vinyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, and combinations thereof.

[0130] According to the present invention, any non-silicone ethylene crosslinking agent can be used. Examples of preferred non-silicone ethylene crosslinking agents are described later in this application.

[0131] According to the present invention, the silicone hydrogel (SiHy) contact lens of the present invention can be produced according to any lens manufacturing method. Those skilled in the art are very well aware of how to prepare SiHy contact lenses. For example, SiHy contact lenses can be produced by conventional “rotational casting molding” as described, for example, in US 3408429, or by a full casting molding process as described in US Patent Nos. 4347198; 5508317; 5583463; 5789464; and 5849810, in static form, or by lathe-like cutting of polymer material buttons, as used in the manufacture of custom contact lenses. In casting molding, a polymerizable composition (i.e., the SiHy lens preparation) is typically dispensed into a mold and cured (i.e., polymerized and / or crosslinked) in the mold used to prepare the SiHy contact lens.

[0132] Lens molds for manufacturing contact lenses (including SiHy contact lenses) are well known to those skilled in the art and are used, for example, in casting molding or rotational casting. For example, a mold (for casting molding) typically includes at least two mold regions (or portions) or half-molds, namely first and second half-molds. The first half-mold defines a first molding (or optical) surface and the second half-mold defines a second molding (or optical) surface. The first and second half-molds are configured to receive each other such that a lens-forming cavity is formed between the first molding surface and the second molding surface. The molding surface of the half-mold is the cavity-forming surface of the mold and is in direct contact with the polymerizable composition.

[0133] Methods for manufacturing mold areas for casting contact lenses are generally well known to those skilled in the art. The methods of the present invention are not limited to any particular method of forming a mold. In fact, any method of forming a mold can be used in the present invention. The first and second half-molds can be formed by various techniques, such as injection molding or lathe machining. Examples of suitable methods for forming half-molds are disclosed in U.S. Patent Nos. 4,444,711; 4,460,534; 5,843,346; and 5,894,002.

[0134] Almost all materials known in the art for manufacturing molds can be used to manufacture molds for producing contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, and PMMA can be used. COC grade 8007-S10 (a clear, amorphous copolymer of ethylene and norbornene from Ticona GmbH, Frankfurt, Germany and Summit, New Jersey, USA), etc. Other materials that allow UV light transmission, such as quartz glass and sapphire, can be used.

[0135] According to the present invention, a polymerizable composition may be introduced (dispensed) into a cavity formed by a mold according to any known method.

[0136] After the polymerizable composition is dispensed into a mold, it is polymerized to produce a SiHy contact lens. Crosslinking can preferably be thermally or photochemically initiated by exposing the polymerizable composition in the mold to spatial confinement of photochemical radiation, so as to crosslink the polymerizable components in the polymerizable composition.

[0137] This allows the mold opening, from which the molded SiHy contact lens can be removed, to occur in a manner known per se.

[0138] Molded SiHy contact lenses can be extracted using a liquid extraction medium to remove unpolymerizable polymerizable components and formed oligomers. According to the invention, the extraction liquid medium is any solvent capable of dissolving organic solvents, unpolymerizable polymerizable materials, and oligomers in dry contact lenses. Water, any organic solvent known to those skilled in the art, or mixtures thereof can be used in this invention. Preferably, the organic solvent used as the extraction liquid medium is water, buffered brine, C1-C3 alkyl alcohols, 1,2-propanediol, polyethylene glycol having a number average molecular weight of about 400 Daltons or less, C1-C6 alkyl alcohols, or combinations thereof.

[0139] After extraction, the silicone hydrogel contact lens can be hydrated in water or an aqueous solution in place of any method known to those skilled in the art to replace the liquid extraction medium.

[0140] Hydrated silicone hydrogel contact lenses can be further subjected to other processes, such as surface treatment, encapsulation in lens packaging with packaging solutions well known to those skilled in the art; sterilization, such as autoclaving at 118°C to 124°C for at least about 30 minutes; and so on.

[0141] Lens packaging (or containers) is well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens packaging can be used in this invention. Preferably, the lens packaging is a blister pack comprising a base and a cover, wherein the cover is removably sealed to the base, and wherein the base includes a cavity for receiving a sterile packaging solution and the contact lens.

[0142] Before being distributed to users, the lenses are packaged in individual containers, sealed, and sterilized (e.g., by autoclaving at approximately 120°C or higher for at least 30 minutes). Those skilled in the art will well understand how to seal and sterilize lens packaging.

[0143] SiHy contact lens formulations may also include other necessary components known to those skilled in the art, such as free radical initiators (e.g., thermal polymerization initiators, photoinitiators), UV-absorbing vinyl monomers, high-energy ultraviolet light (“HEVL”), absorbent vinyl monomers, visible colorants (e.g., reactive dyes, polymerizable dyes, pigments), antimicrobial agents (e.g., preferably silver nanoparticles), bioactive agents, leachable polymeric wetting agents (e.g., non-polymerizable hydrophilic polymers), leachable tear stabilizers (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, neurosphingolipids, etc.), and mixtures thereof.

[0144] Any thermal polymerization initiator can be used in this invention. Suitable thermal polymerization initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azobis(alkyl- or cycloalkylnitrile), persulfates, percarbonates, or mixtures thereof. Examples of preferred thermal polymerization initiators include, but are not limited to, benzoyl peroxide, tert-butyl peroxide, tert-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-tert-butyl-dipexyl phthalate, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, and di(4-tert-butylcyclohexyl)peroxydicarbonate (Perkadox). 16S), di(2-ethylhexyl)peroxydicarbonate, tert-butyl peroxy ester neopentanoate (Lupersol 11); tert-butyl peroxy-2-ethylhexanoate (Trigonox 21-C50), 2,4-pentanedione peroxide, dicumyl peroxide, peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2′-azobis(4-methoxy-2,4-dimethylpentanonitrile) (VAZO 33), 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAZO 44), 2,2′-azobis(2-amidinylpropane) dihydrochloride (VAZO 50), 2,2′-azobis(2,4-dimethylpentanonitrile) (VAZO 52), 2,2′-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2′-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarboxylonitrile) (VAZO 88); 2,2′-azobis(2-cyclopropylpropionitrile), 2,2′-azobis(methyl isobutyrate), 4,4′-azobis(4-cyanopentanoic acid), and combinations thereof. Preferably, the thermal initiator is 2,2′-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0145] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and Darocur and Irgacur types, with Darocur being preferred. and Darocur germanium-based Norrish type I photoinitiators (e.g., those described in US 7,605,190). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyl diphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propanylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butanylphosphine oxide. Reactive photoinitiators, for example, that can be incorporated into macromonomers or used as specific monomers, are also suitable. Examples of reactive photoinitiators are those disclosed in EP 632 329. Preferably, SiHy lens preparations for manufacturing SiHy contact lenses comprise at least one photoinitiator that can be initiated by visible light, such as benzoylphosphine oxide photoinitiators, germanium-based Norrish type I photoinitiators, or combinations thereof.

[0146] The polymerizable composition (SiHy lens assembly) can be a solvent-free, transparent liquid prepared by mixing all polymerizable components with other necessary components; or a solution prepared by dissolving all desired components in any suitable solvent known to those skilled in the art, such as water and a mixture of one or more water-miscible organic solvents, an organic solvent, or a mixture of one or more organic solvents. The term "solvent" refers to a chemical that cannot participate in free radical polymerization.

[0147] Solvent-free SiHy lens formulations typically contain at least one blended ethylene monomer as a reactive solvent to dissolve all other polymerizable components of the solvent-free SiHy lens formulation. Examples of preferred blended ethylene monomers are described later in this application. Preferably, methyl methacrylate is used as the blended ethylene monomer in the preparation of solvent-free SiHy lens formulations.

[0148] Any solvent can be used in this invention. Examples of preferred organic solvents include, but are not limited to, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, and amyl acetate. Methyl lactate, ethyl lactate, isopropyl lactate, dichloromethane, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol, and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-pentanol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro- 2-Methyl-2-propanol, 2-Methyl-2-heptanol, 2-Methyl-2-octanol, 2-2-Methyl-2-nonanol, 2-Methyl-2-decanol, 3-Methyl-3-hexanol, 3-Methyl-3-heptanol, 4-Methyl-4-heptanol, 3-Methyl-3-octanol, 4-Methyl-4-octanol, 3-Methyl-3-nonanol, 4-Methyl-4-nonanol, 3-Methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1 -Ethylcyclopentanol, 1-Ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof.

[0149] SiHy lens formulations (i.e., polymerizable compositions) can be thermo-cured or photochemically cured (polymerized) as known to those skilled in the art, preferably in a mold for casting contact lenses.

[0150] Thermal polymerization can be conveniently carried out, for example, at temperatures ranging from 25°C to 120°C, and preferably from 40°C to 100°C. The reaction time can vary over a wide range, but conveniently, for example, from 1 to 24 hours, or preferably from 2 to 12 hours. It is advantageous to pre-degas the components and solvents used in the polymerization reaction and to carry out the copolymerization reaction under an inert atmosphere, such as nitrogen or argon.

[0151] Photochemical polymerization can then be initiated by photochemical radiation, such as light of suitable wavelengths, particularly UV or visible light. Therefore, spectral requirements can be controlled, if appropriate, by adding suitable photosensitizers.

[0152] Although various embodiments of the invention have been described using specific terms, apparatus, and methods, such descriptions are for illustrative purposes only. The language used is descriptive rather than limiting. It should be understood that changes and variations can be made by those skilled in the art without departing from the spirit or scope of the invention as set forth in the following claims. Furthermore, it should be understood that various aspects of the various embodiments can be interchanged in whole or in part, or can be combined and / or used in any way, as described below:

[0153] 1. A hydrophilic polydiorganosiloxane ethylene crosslinking agent, comprising:

[0154] (1) A polydiorganosiloxane segment comprising a dimethylsiloxane unit and at least one hydrophilic siloxane unit, the hydrophilic siloxane unit having a methyl substituent and an organic substituent having a phosphorylcholine moiety; and

[0155] (2) Alkenyl bond unsaturated groups.

[0156] 2. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 1, wherein the polydiorganosiloxane segment comprises 6 to 500 dimethylsiloxane units.

[0157] 3. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 1, wherein the polydiorganosiloxane segment comprises 10 to 450 dimethylsiloxane units.

[0158] 4. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 1, wherein the polydiorganosiloxane segment comprises 15 to 400 dimethylsiloxane units.

[0159] 5. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 1, wherein the polydiorganosiloxane segment comprises 20 to 350 dimethylsiloxane units.

[0160] 6. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 5, wherein the polydiorganosiloxane segment comprises 3 to 80 hydrophilic siloxane units.

[0161] 7. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 5, wherein the polydiorganosiloxane segment comprises 5 to 70 hydrophilic siloxane units.

[0162] 8. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 5, wherein the polydiorganosiloxane segment comprises 7 to 60 hydrophilic siloxane units.

[0163] 9. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 5, wherein the polydiorganosiloxane segment comprises 9 to 50 hydrophilic siloxane units.

[0164] 10. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 9, wherein the olefinic unsaturated group is (meth)acryloyl.

[0165] 11. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 10, wherein the molar ratio of the hydrophilic siloxane unit to the dimethylsiloxane unit is from about 0.002 to about 0.50.

[0166] 12. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 10, wherein the molar ratio of the hydrophilic siloxane unit to the dimethylsiloxane unit is from about 0.002 to about 0.20.

[0167] 13. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 10, wherein the molar ratio of the hydrophilic siloxane unit to the dimethylsiloxane unit is from about 0.004 to about 0.1.

[0168] 14. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 10, wherein the molar ratio of the hydrophilic siloxane unit to the dimethylsiloxane unit is from about 0.004 to about 0.05.

[0169] 15. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 14, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent has a number average molecular weight of at least 1000 Daltons.

[0170] 16. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 14, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent has a number average molecular weight from 1,500 Daltons to 80,000 Daltons.

[0171] 17. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 14, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent has a number average molecular weight from 2,000 to 50,000 Daltons.

[0172] 18. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 14, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent has a number average molecular weight from 2,500 to 25,000 Daltons.

[0173] 19. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 18, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent is defined by formula (1) or (2).

[0174]

[0175]

[0176] in:

[0177] υ1 is an integer from 6 to 500;

[0178] ω1 is an integer from 3 to 80;

[0179] γ1 is an integer from 1 to 78;

[0180] E1 is Monovalent groups;

[0181] E2 is Monovalent groups;

[0182] R0 is either hydrogen or methyl;

[0183] a1 is zero or 1;

[0184] X0 is either O or NR N1 ;

[0185] R N1 It is hydrogen or C1-C6 alkyl;

[0186] L0 is a C2-C8 alkylene divalent group, or -L0′-X1-L0″-. divalent groups;

[0187] L0' is a C2-C8 alkylene divalent group;

[0188] "L0" is a C3-C8 alkylene divalent group;

[0189] X1 is -O-, -NR N1 -、-NHCOO-、-OCONH-、-CONR N1 -or-NR N1 CO-;

[0190] q1 is an integer from 1 to 20;

[0191] R PC yes Monovalent groups;

[0192] L e It is -CH2-CHR0-R1-, -C3H6-O-R2-, divalent groups;

[0193] R1 is a C1-C chain, whether straight or branched. 10 alkylene divalent groups;

[0194] R2 is a straight or branched C3-C. 10 alkylene divalent groups;

[0195] R3 is a C1-C4 alkylene divalent group that is either directly bonded, straight-chain, or branched;

[0196] n is an integer from 1 to 5;

[0197] R' and R” are independently C1-C8 alkyl or C1-C8 hydroxyalkyl;

[0198] R”' is a C1-C8 alkylene divalent group;

[0199] T1 is hydrogen, hydroxyl, or C1-C4 alkoxy; and

[0200] T2 is a C1-C8 alkyl, C1-C8 hydroxyalkyl, R4-O-R5-, or -R PC -T1;

[0201] R4 is a C1-C4 alkyl group; and

[0202] R5 is a C2-C8 alkylene divalent group.

[0203] 20. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 19, wherein in formula (1) or (2), υ1 is an integer from 10 to 450.

[0204] 21. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 19, wherein in formula (1) or (2), υ1 is an integer from 15 to 400.

[0205] 22. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 19, wherein in formula (1) or (2), υ1 is an integer from 20 to 350.

[0206] 23. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 19 to 22, wherein, in formula (1) or (2), ω1 is an integer from 5 to 70.

[0207] 24. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 19 to 22, wherein, in formula (1) or (2), ω1 is an integer from 7 to 60.

[0208] 25. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 19 to 22, wherein, in formula (1) or (2), ω1 is an integer from 9 to 50.

[0209] 26. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 19 to 25, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent is represented by formula (1).

[0210] 27. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 26, wherein a1 is zero in formula (1).

[0211] 28. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 27, wherein X0 is O in formula (1).

[0212] 29. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 27, wherein, in formula (1), X0 is NR N1 .

[0213] 30. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 19 to 25, wherein the hydrophilic polydiorganosiloxane ethylene crosslinking agent is represented by formula (2).

[0214] 31. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 30, wherein X0 is O in formula (2).

[0215] 32. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in Example 30, wherein, in formula (2), X0 is NR N1 .

[0216] 33. A silicone hydrogel contact lens comprising a crosslinked polymer material, said crosslinked polymer material comprising units of a hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of Examples 1 to 32.

[0217] 34. The silicone hydrogel contact lens as described in Example 33, wherein when fully hydrated, the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 40 bar, a water content of from about 15% to about 70% by weight, and an elastic modulus of from about 0.20 MPa to about 1.8 MPa.

[0218] 35. The silicone hydrogel contact lens as described in Example 33 or 34, wherein when fully hydrated, the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 60 bar.

[0219] 36. The silicone hydrogel contact lens as described in Example 33 or 34, wherein when fully hydrated, the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 70 bar.

[0220] 37. The silicone hydrogel contact lens as described in Example 33 or 34, wherein when fully hydrated, the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 80 bar.

[0221] 38. The silicone hydrogel contact lens as described in any one of Examples 33 to 37, wherein when fully hydrated, the silicone hydrogel contact lens has a water content of from about 20% to about 70% by weight.

[0222] 39. The silicone hydrogel contact lens as described in any one of Examples 33 to 38, wherein when fully hydrated, the silicone hydrogel contact lens has a water content of from about 25% to about 65% by weight.

[0223] 40. The silicone hydrogel contact lens as described in any one of Examples 33 to 38, wherein when fully hydrated, the silicone hydrogel contact lens has a water content of from about 30% to about 60% by weight.

[0224] 41. The silicone hydrogel contact lens as described in any one of Examples 33 to 40, wherein when fully hydrated, the hydrophilic silicone hydrogel contact lens has an elastic modulus from about 0.25 MPa to about 1.5 MPa.

[0225] 42. The silicone hydrogel contact lens as described in any one of Examples 33 to 40, wherein when fully hydrated, the hydrophilic silicone hydrogel contact lens has an elastic modulus from about 0.3 MPa to about 1.2 MPa.

[0226] 43. The silicone hydrogel contact lens as described in any one of Examples 33 to 40, wherein when fully hydrated, the hydrophilic silicone hydrogel contact lens has an elastic modulus from about 0.4 MPa to about 1.0 MPa.

[0227] 44. The silicone hydrogel contact lens as described in any one of Examples 33 to 43, wherein the silicone hydrogel contact lens comprises at least one unit of a polymerizable component containing silicone and at least one unit of a hydrophilic ethylene monomer.

[0228] 45. The silicone hydrogel contact lens as described in any one of Examples 33 to 44, wherein the silicone hydrogel contact material comprises a repeating unit of at least one silicone-containing vinyl monomer selected from the group consisting of: vinyl monomers having bis(trialkylsilyloxy)alkylsilyl groups, vinyl monomers having tri(trialkylsilyloxy)silyl groups, polysiloxane vinyl monomers, 3-methacryloyloxypropylpentamethyldisiloxane, tert-butyldimethyl-siloxane-ethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0229] 46. ​​The silicone hydrogel contact lens as described in any one of Examples 33 to 44, wherein the silicone hydrogel contact material comprises at least one repeating unit of a silicone-containing vinyl monomer having formula (M1) or (M2).

[0230]

[0231] Where: a M1 It is zero or 1; R M0 It is H or methyl; X M0 Is it O or NR? M1 L M1 It is a C2-C8 alkylene divalent group or a divalent group -L M1 ′-X M1 -L M1 "-、 L M1 ′-X M1 ′-CH2-CH(OH)-CH2-OL M1 "-,or L M1 ' is a C2-C8 alkylene divalent group having zero or one hydroxyl group; L M1 " is a C3-C8 alkylene divalent group having zero or one hydroxyl group; X M1 It is O, NR M1 NHCOO, OCONH, CONR M1, or NR M1 CO;R M1 It is H or a C1-C4 alkyl group having 0 to 2 hydroxyl groups; R t1 and R t2 Each of them is independently a C1-C6 alkyl group; X M1 ' is 0 or NR1; v1 is an integer from 1 to 30; v2 is an integer from 0 to 30; n1 is an integer from 3 to 40; and r1 is an integer of 2 or 3.

[0232] 47. The silicone hydrogel contact lens as described in Examples 45 or 46, wherein the at least one silicone-containing vinyl monomer comprises: tri(trimethylsilyloxy)methoxypropyl acrylate, [3-(meth)acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsilyloxy)methylsilane, [3-(meth)acryloyloxy-2-hydroxypropoxy]propylbis(trimethylsilyloxy)butylsilane, 3-(meth)acryloyloxy-2-(2-hydroxyethoxy)-propoxy)propylbis(trimethylsilyloxy)methylsilane, 3-(meth)acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsilyloxy)methylsilane, Tris(trimethylsilyloxy)silane, N-[tris(trimethylsilyloxy)silylpropyl]-(methyl)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)propyl)-2-methyl(methyl)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)propyl)(methyl)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl)-2-methylacrylamide, Silyloxy)silyl)propoxy)propyl)(methyl)acrylamide, N-[tris(dimethylpropylsilyloxy)silylpropyl]-(methyl)acrylamide, N-[tris(dimethylphenylsilyloxy)silylpropyl](methyl)acrylamide, N-[tris(dimethylethylsilyloxy)silylpropyl](methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy] [alkyl)propoxy)-propyl](methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl](methyl)acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)-propyl]-2-methyl(methyl)acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)-propyl](methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloyloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propyl vinylcarbamate, 3-(vinyloxycarbonylthio)-propyl-tris(trimethyl-siloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl allylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, or combinations thereof.

[0233] 48. The silicone hydrogel contact lens as described in any one of Examples 45 to 47, wherein the at least one silicone-containing vinyl monomer comprises: α-(meth)acryloyloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-(meth)acryloyloxy-2-hydroxypropoxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-(2-hydroxy-methacryloyloxypropoxypropyl)-ω-C1-C4-alkyl-decamethylpentasiloxane, α-[3-(meth)acryloyloxyethoxy-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxy-propoxy-2-hydroxy... [3-(meth)acryloyloxyisopropoxy-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxybutoxy-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxyethylamino-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxypropylamino-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-( [Meth)acryloyloxy-butylamino-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, [α-(meth)acryloyloxy-(polyvinyloxy)-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, [α-[(meth)acryloyloxy-2-hydroxypropoxy-ethoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, [α-[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, [α-[(meth)acryloyloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane] Siloxanes, α-[(meth)acryloyloxy-2-hydroxypropoxy-(polyvinyloxy)propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxanes, α-(meth)acryloylaminopropoxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxanes, α-N-methyl-(meth)acryloylaminopropoxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxanes, α-[3-(meth)acrylamidoethoxy-2-hydroxypropoxy-propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxanes, α-[3-(meth)acrylamidopropoxy-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxanes,α-[3-(meth)acrylamidoisopropoxy-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidobutoxy-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamido-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl polydimethylsiloxane, α-[3-[N-methyl-(meth)acrylamido]-2-hydroxypropoxypropyl]-terminated ω-C1-C4-alkyl-terminated Polydimethylsiloxane, N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(methyl)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(methyl)acrylamide, (methyl)acrylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, α-vinyl carbonate-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-vinyl carbamate-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, or mixtures thereof.

[0234] 49. The silicone hydrogel contact lens as described in any one of Examples 33 to 48, wherein the silicone hydrogel material comprises repeating units of at least one polysiloxane ethylene crosslinking agent.

[0235] 50. The silicone hydrogel contact lens as described in Example 49, wherein the at least one polysiloxane vinyl crosslinking agent comprises: di-(meth)acryloyl-terminated polydimethylsiloxane, di-vinyl carbonate-terminated polydimethylsiloxane; di-vinyl carbamate-terminated polydimethylsiloxane; N,N,N',N'-tetratetra(3-methacryloyl-2-hydroxypropyl)-α,ω-bis-3-aminopropyl-polydimethylsiloxane, or combinations thereof.

[0236] 51. The silicone hydrogel contact lens as described in Examples 49 or 50, wherein the at least one polysiloxane ethylene crosslinking agent comprises an ethylene crosslinking agent having formula (I).

[0237]

[0238] in:

[0239] d1 is an integer from 30 to 500 and d2 is an integer from 1 to 75, provided that d2 / d1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about 0.12, even more preferably from about 0.045 to about 0.10);

[0240] X 01 Is it O or NR? IN , where RIN It is hydrogen or C1-C 10 -alkyl;

[0241] R I0 It is hydrogen or methyl;

[0242] R I1 and R I2 Independent of each other: substituted or unsubstituted C1-C 10 alkylene divalent group or -R I4 -OR I5 - a divalent group, wherein R I4 and R I5 C1-C are either substituted or unsubstituted, independent of each other. 10 alkylene divalent groups;

[0243] R I3 It is a monovalent group having any one of formulas (Ia) to (Ie).

[0244]

[0245] k1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5;

[0246] R I6 It is hydrogen or methyl;

[0247] R I7 It is a C2-C6 hydrocarbon group with a valence of (m2+1);

[0248] R I8 It is a C2-C6 hydrocarbon group with a valence of (m4+1);

[0249] R I9 It is ethyl or hydroxymethyl;

[0250] R I10 It is methyl or hydroxymethyl;

[0251] R I11 It is either hydroxyl or methoxy;

[0252] X I1 It is a -S-sulfur bond or -NR I12 - tertiary amino bond, where R I12 It is C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl; and

[0253] X I2 yes The amide bond, where R I13 It is hydrogen or C1-C 10 alkyl.

[0254] 52. The silicone hydrogel contact lens as described in any one of Examples 49 to 51, wherein the at least one polysiloxane ethylene crosslinking agent comprises: (1) an ethylene crosslinking agent comprising a single polydiorganosiloxane segment and two terminal olefinic unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, and vinyl carbamate groups; and / or (2) a chain-extended polysiloxane ethylene crosslinking agent comprising at least two polydiorganosiloxane segments and a covalent linker between each pair of polydiorganosiloxane segments and two terminal olefinic unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, and vinyl carbamate groups.

[0255] 53. The silicone hydrogel contact lens as described in any one of Examples 49 to 52, wherein the at least one polysiloxane vinyl crosslinking agent comprises: α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxyethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω -Bis[3-(meth)acryloyloxy-isopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxanes, α,ω-bis[3-(meth)acryloyloxybutoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxanes, α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxanes, α,ω-bis[3-(meth)acrylamidopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxanes, α,ω-bis[3-(meth)acrylamidoisopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxanes, α,ω-bis[3-(meth)acrylamidobut ... [3-(meth)acryloyloxyethylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxybutylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxybutylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxyethylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxybutyl ... Acrylamide-butylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropoxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropoxy-(polyvinyloxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-Bis[(meth)acryloyloxyethylamino-carbonyloxy-(polyvinyloxy)propyl]-terminated polydimethylsiloxanes, or combinations thereof.

[0256] 54. The silicone hydrogel contact lens as described in any one of Examples 33 to 53, wherein the silicone hydrogel material comprises repeating units of at least one hydrophilic vinyl monomer.

[0257] 55. The silicone hydrogel contact lens as described in Example 54, wherein the at least one hydrophilic vinyl monomer comprises: (1) alkyl (meth)acrylamide selected from the group consisting of: (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-3-methoxypropyl (meth)acrylamide, and combinations thereof; (2) hydroxyl-containing acrylic monomer selected from the group consisting of: N-2-hydroxyethyl (meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide. Amides, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glyceryl methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (3) carboxyl-containing propylene selected from the group consisting of Acid monomers: 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidovalerate, 4-(meth)acrylamidobutyric acid, 3-(meth)acrylamido-2-methylbutyric acid, 3-(meth)acrylamido-3-methylbutyric acid, 2-(meth)acrylamido-2-methyl-3,3-dimethylbutyric acid, 3-(meth)acrylamidohexanoic acid, 4-(meth)acrylamido-3,3-dimethylhexanoic acid, and combinations thereof; (4) amino-containing acrylic monomers selected from the group consisting of: N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N- 2-Ethylaminoethyl (meth)acrylamide, N-2-dimethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, N-3-dimethylaminopropyl (meth)acrylamide, 2-aminoethyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-ethylaminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate trimethylammonium hydrochloride, dimethylaminoethyl (meth)acrylate, and combinations thereof;(5) N-vinylamide monomers selected from the group consisting of: N-vinylpyrrolidone (also known as N-vinyl-2-pyrrolidone), N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidine Ketones (also known as N-vinyl-2-piperidinone), N-vinyl-3-methyl-2-piperidinone, N-vinyl-4-methyl-2-piperidinone, N-vinyl-5-methyl-2-piperidinone, N-vinyl-6-methyl-2-piperidinone, N-vinyl-6-ethyl-2-piperidinone, N-vinyl-3,5-dimethyl-2-piperidinone, N-vinyl-4,4-dimethyl-2-piperidinone, N-vinylcaprolactam (also known as N-vinyl-2-caprolactam), N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl- 7-Methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof; (6) a methylene-containing pyrrolidone monomer selected from the group consisting of: 1-methyl-3-methylene-2-pyrrolidone. Pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof;(7) Acrylic monomers having a C1-C4 alkoxyethoxy group and selected from the group consisting of: ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4-alkoxy poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (8) Vinyl ether monomers selected from the group consisting of: ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether Ethers, tetra(ethylene glycol) monovinyl ethers, poly(ethylene glycol) monovinyl ethers, ethylene glycol methyl vinyl ethers, di(ethylene glycol) methyl vinyl ethers, tri(ethylene glycol) methyl vinyl ethers, tetra(ethylene glycol) methyl vinyl ethers, poly(ethylene glycol) methyl vinyl ethers, and combinations thereof; (9) allyl ether monomers selected from the group consisting of: ethylene glycol monoallyl ethers, di(ethylene glycol) monoallyl ethers, tri(ethylene glycol) monoallyl ethers, tetra(ethylene glycol) monoallyl ethers, poly(ethylene glycol) monoallyl ethers, ethylene glycol methyl allyl ethers, di(ethylene glycol) methyl allyl ethers, tri(ethylene glycol) methyl allyl ethers, tetra(ethylene glycol) methyl allyl ethers, poly(ethylene glycol) methyl allyl ethers, and combinations thereof;(10) Ethylene monomers containing phosphorylcholine selected from the group consisting of: (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonium)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonium)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonium)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonium)ethyl phosphate, 5-( (Meth)acryloyloxy)pentyl-2'-(trimethylammonium)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonium)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonium)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonium)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonium)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonium)ethyl phosphate, 2- ((meth)acryloyloxy)butyl-2'-(trimethylammonium)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonium)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonium)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonium)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonium)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonium)ethyl phosphate, 2-(allyloxycarbonyl)ethyl -2'-(trimethylammonium)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonium)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonium)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonium)ethyl phosphate, and combinations thereof; (11) allyl alcohol; (12) N-2-hydroxyethyl vinylcarbamate; (13) N-carboxyvinyl-β-alanine (VINAL); (14) N-carboxyvinyl-α-alanine; (15) or combinations thereof.

[0258] 56. The silicone hydrogel contact lens as described in Examples 54 or 55, wherein the at least one hydrophilic vinyl monomer comprises N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or a combination thereof.

[0259] 57. The silicone hydrogel contact lens as described in any one of Examples 54 to 56, wherein the at least one hydrophilic vinyl monomer comprises N,N-dimethyl (meth)acrylamide.

[0260] 58. The silicone hydrogel contact lens as described in any one of Examples 54 to 57, wherein the at least one hydrophilic vinyl monomer comprises: N-2-hydroxyethyl (meth)acrylamide, N,N-bis(hydroxyethyl) (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glyceryl methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, or combinations thereof.

[0261] 59. The silicone hydrogel contact lens as described in any one of Examples 33 to 58, wherein the silicone hydrogel material comprises repeating units of at least one non-silicone vinyl crosslinking agent.

[0262] 60. The silicone hydrogel contact lens as described in Example 59, wherein the at least one non-silicone vinyl crosslinking agent comprises: ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, etc. Di-(meth)acrylates of alcohols, 1,3-diglycerides of glycerols, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylates, bis[2-(meth)acryloyloxyethyl]phosphates, trimethylolpropane di-(meth)acrylates, and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine N,N-Di(meth)acryloyl-N-ethylamine, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-dihydroxyethylenebis(meth)acrylamide, N,N'-propylenebis(meth)acrylamide, N,N'-2-hydroxypropylenebis(meth)acrylamide, N,N'-2,3-dihydroxybutylbis(meth)acrylamide, 1,3-bis(meth)acrylamide propane -2-yl dihydrophosphate, piperazine diacrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, or combinations thereof.

[0263] 61. The silicone hydrogel contact lens as described in any one of Examples 33 to 60, wherein the silicone hydrogel material comprises repeating units of at least one blended vinyl monomer.

[0264] 62. The silicone hydrogel contact lens as described in Example 61, wherein the at least one blended vinyl monomer comprises: (meth)acrylic acid C1-C 10 Alkyl esters, cyclopentyl acrylates, cyclohexyl methacrylates, cyclohexyl acrylates, isobornyl acrylate (meth)acrylate, styrene, 4,6-trimethylstyrene (TMS), tert-butylstyrene (TBS), trifluoroethyl acrylate (meth)acrylate, hexafluoro-isopropyl acrylate (meth)acrylate, hexafluorobutyl acrylate (meth)acrylate, or combinations thereof.

[0265] 63. The silicone hydrogel contact lens as described in Example 61 or 62, wherein the at least one blended vinyl monomer comprises methyl methacrylate.

[0266] The foregoing disclosure will enable those skilled in the art to practice this invention. Various modifications, variations, and combinations can be made to the various embodiments described herein. To enable the reader to better understand the specific embodiments and advantages thereof, reference is recommended to the following examples. It is intended that this specification and the examples be considered exemplary.

[0267] Example 1

[0268] Oxygen permeability measurement

[0269] Unless otherwise specified, determine the oxygen permeability (Dk / t) and inherent (or edge-corrected) oxygen permeability (Dk) of the lens and lens material according to the procedure described in ISO 18369-4. i or Dk c ).

[0270] equilibrium moisture content

[0271] The equilibrium water content (EWC) of the contact lens is measured as follows.

[0272] The amount of water (expressed as a percentage by weight) present in a fully hydrated hydrogel contact lens in saline solution at room temperature was determined. After the lenses were blotted dry with a fabric, they were quickly stacked and the stack transferred to an aluminum pan on an analytical balance. Typically, five lenses were used for each sample pan (5). The hydrated weight of the pan plus the lenses was recorded. The pan was covered with aluminum foil. The pan was placed in a laboratory oven at 100°C ± 2°C and dried for 16–18 hours. The pan was removed from the oven with the lenses and cooled in a desiccator for at least 30 minutes. The individual pans were removed from the desiccator and the aluminum foil was removed. The pan with the dried lens sample was weighed on an analytical balance. This was repeated for all pans. The wet and dry weights of the lens samples can be calculated by subtracting the weight of the empty weighing pan.

[0273] elastic modulus

[0274] The elastic modulus of the contact lens was determined using an MTS insight instrument. First, the contact lens was cut into a 3.12 mm wide strip using a Precision Concept two-stage cutter. Five thickness values ​​were measured within a 6.5 mm gauge length. The strip was mounted on the instrument holder and immersed in PBS (phosphate-buffered saline) at a controlled temperature of 21 °C ± 2 °C. A 5 N load cell was typically used for testing. Constant force and velocity were applied to the sample until it fractured. Force and displacement data were collected using TestWorks software. The elastic modulus value was calculated using TestWorks software, which is the slope or tangent of the stress-strain curve in the elastic deformation region, close to zero elongation.

[0275] Example 2

[0276] Polydiorganosiloxane ethylene crosslinking agents having side-group reactive functional groups (e.g., primary hydroxyl groups) are prepared according to the procedure shown in Scheme 1.

[0277]

[0278] Option 1

[0279] Synthetic precursors

[0280] 275.9 g of octamethylcyclotetrasiloxane (MW296.62), 12.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane (MW240.51), 15.3 g of 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane (MW386.63), and 0.9 g of trifluoromethanesulfonic acid (MW150.08) were weighed into a 500 mL round-bottom flask. After the reaction was run at 35 °C for 24 h, 170 mL of 0.5% sodium bicarbonate was added. The collected organic fraction was further extracted five times with deionized water (170 mL per cycle). Anhydrous MgSO4 was added to the collected organic solution, followed by approximately 350 mL of additional CHCl3, and the solution was stirred overnight. After filtration, the solvent was removed via a rotary evaporator, followed by high vacuum. 102 g of the final product (the precursor) was obtained.

[0281] Hydrosilylation reaction with allyloxyethanol

[0282] A small reactor was connected to a heater and an air condenser with a drying tube. 21 g of toluene, 15 g or more of the precursor, and 3.88 g of allyloxyethanol were added to the reactor. After the solution temperature stabilized at 30 °C, 152 μL of Karstedt catalyst (2 pt% in xylene) was added. 100% Si-H conversion based on IR was achieved after 2 h. The solution was then transferred to a flask, concentrated using a rotary evaporator, and subsequently precipitated three times in an acetonitrile / water mixture (75 / 25). After solvent removal via a rotary evaporator followed by high vacuum, 10 g of turbid liquid was obtained. Molecular weight was determined by H... 1 NMR spectroscopy determination.

[0283] Example 3

[0284] Hydrophilic polydiorganosiloxane ethylene crosslinking agents are prepared according to the procedure shown in Scheme 2.

[0285]

[0286] Option 2

[0287] The synthesis of hydrophilic polydiorganosiloxane ethylene crosslinking agent 1 is accomplished by reacting hydroxyl-containing PDMS2 with commercially available 2-chloro-2-oxo-1,3,2-dioxophosphazenecyclopentane (COP) in THF (or a compatible solvent) at a low temperature (e.g., about -10°C) to generate intermediate 3, which is then reacted with trimethylamine in THF (or a compatible solvent) at a slightly elevated temperature (e.g., 50°C). The reaction conditions for preparing hydrophilic polydiorganosiloxane vinyl crosslinking agents can follow procedures similar to those described in the literature for the synthesis of 2-(methacryloyloxy)ethyl-2-(trimethylammonium)ethyl phosphate (MPC) (see Takashi Umeda, Tadao Nakaya, Minoru Imoto, Makromol. Chem., Rapid Commun. 3, 457-459 (1982) and Kazuhiko Ishihara, Tomoko Ueda, Nobuko Nakabayashi, Polymer Journal, 22, 355-360 (1990)) and those illustrated in Example 4, excluding those procedures involved in the reaction between PDMS 3-A containing cyclic vinyl phosphate and dimethylaminopropylmethacrylamide.

[0288] The hydrophilic polydiorganosiloxane ethylene crosslinking agent can then be purified and characterized according to the experimental procedure described in Example 4.

[0289] Example 4

[0290] The reactions conducted in Example 4 are summarized in Scheme 3 below:

[0291]

[0292] Option 3

[0293] The 500 mL jacketed reactor, equipped with a mechanical stirrer, thermocouple, nitrogen feed (attached to the condenser), septum, and condenser, was cooled to -10 °C and purged with nitrogen at a rate of 100 mL / min for 60 min.

[0294] Hydroxyl-containing PDMS2-A (6.10 g, MW ~10,000 g / mol, x = 88, y = 23) was placed in a conical flask equipped with a magnetic stirrer and the flask was covered with a rubber septum. Anhydrous THF (75 mL) was inserted into the flask through the septum tube. The contents of the flask were stirred at room temperature until all the polymer was dissolved, and then the flask was inserted into the reactor. Triethylamine (1.45 g, 14.33 mmol) was added to the reactor via a syringe.

[0295] 2-Chloro-2-oxo-1,3,2-dioxophosphazenecyclopentane (COP) (2.03 g, 14.25 mmol) was dissolved in 30 mL of THF and loaded into a 500 mL Hamilton GasTight syringe equipped with a 20-inch stainless steel needle. The syringe was attached to a Harvard PHD infusion pump, and the stainless steel needle was inserted into the reactor via a rubber septum.

[0296] During a 50-minute process, a solution of COP in THF was added via a syringe pump, while the reactor temperature was maintained between -10°C and -8°C. After the addition of COP, the reaction mixture was stirred at approximately -8°C for another 2 hours to form PDMS 3-A containing cyclic vinyl phosphate. During this period, a significant amount of triethylammonium hydrochloride precipitated. After stirring at -8°C for 2 hours, the reaction temperature was raised to 25°C, and 20 mL of dimethylaminopropylmethacrylamide (0.45 g, 2.64 mmol) in THF was added to the reactor. The reaction temperature was raised to 50°C, and the mixture was stirred for 18 hours. The reaction mixture was then cooled to 0°C, and a solution of trimethylamine in THF (1.0 M, 20 mL, 20 mmol) was added via syringe. The mixture was stirred at 50°C for 6 hours, then the reactor temperature was lowered to 0°C, and an additional amount of trimethylamine solution in THF (10 mL) was added. The reaction temperature was raised to 50°C, and the mixture was stirred for another 23 hours.

[0297] The contents of the reactor were transferred to a beaker. The triethylammonium hydrochloride precipitated in the first step was filtered off and washed with THF. 1-Propanol was added to the filtrate and subjected to rotary evaporation. Evaporation was continued with the gradual addition of 1-propanol until all THF was evaporated. The modified polymer in 1-propanol was purified by dialysis through a 1 kDa MWCO regenerated cellulose membrane. Dialysis was initiated in a 50:50 1-propanol / water solvent system and gradually switched to pure DI water. After dialysis, 436 g of the polymer aqueous solution was collected. This solution was filtered through a Schott funnel with a porosity of 3 and concentrated on a rotary evaporator until 1.8% solids were reached. After evaporation, a total of 250 g of 1.8% solution was obtained.

[0298] Further concentration of the 1.8% polymer aqueous solution resulted in the polymer precipitating as a white, rubbery agglomerate. Adding 1-propanol / water redissolved the agglomerate, but this process was lengthy; therefore, it is recommended to stop polymer concentration when the solution begins to become slightly cloudy.

[0299] pass 31P NMR (peak at -0.09 ppm) and 1 ¹H NMR (at 5.637 and 5.390 ppm (methacrylamide) and 3.126 ppm and 3.113 ppm ((-N) + (CH3)3 and (-N) + The peak at (CH3)2-CH2- confirms the formation of the desired product.

[0300] All publications, patents and patent applications cited above are incorporated herein by reference in their entirety.

Claims

1. A hydrophilic polydiorganosiloxane ethylene crosslinking agent, comprising: (1) A polydiorganosiloxane segment comprising a dimethylsiloxane unit and at least one hydrophilic siloxane unit, the hydrophilic siloxane unit having a methyl substituent and an organic substituent having a phosphorylcholine moiety; and (2) At least two olefinic unsaturated groups, in, The molar ratio of the hydrophilic siloxane unit to the dimethylsiloxane unit is from 0.004 to 0.

05. The hydrophilic polydiorganosiloxane ethylene crosslinking agent is defined by formula (2). in: υ1 is an integer from 20 to 350; ω1 is an integer from 9 to 50; γ1 is an integer from 7 to 48; E2 is Monovalent groups; R0 is either hydrogen or methyl; X0 is O or NR N1 ; R N1 It is hydrogen or C1-C6 alkyl; q1 is an integer from 1 to 20; R PC yes Monovalent groups; L e yes , , , , ,or divalent groups; R1 is a C1-C chain, whether straight or branched. 10 alkylene divalent groups; R2 is a straight or branched C3-C. 10 alkylene divalent groups; R3 is a C1-C4 alkylene divalent group that is either directly bonded, straight-chain, or branched; n is an integer from 1 to 5; R' and R” are independently C1-C8 alkyl or C1-C8 hydroxyalkyl; R”' is a C1-C8 alkylene divalent group; T1 is hydrogen, hydroxyl, or C1-C4 alkoxy; and T2 is a C1-C8 alkyl, C1-C8 hydroxyalkyl, R4-O-R5-, or -R PC -T1; R4 is a C1-C4 alkyl group; and R5 is a C2-C8 alkylene divalent group.

2. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in claim 1, wherein, In equation (2), X0 is O.

3. The hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in claim 1, wherein, In equation (2), X0 is NR N1 .

4. A silicone hydrogel contact lens comprising a crosslinked polymer material, said crosslinked polymer material comprising units of a hydrophilic polydiorganosiloxane ethylene crosslinking agent as described in any one of claims 1 to 3.

5. The silicone hydrogel contact lens as described in claim 4, wherein, The crosslinked polymer material comprises repeating units of at least one silicone-containing polymerizable component other than a hydrophilic polydiorganosiloxane ethylene crosslinking agent and repeating units of at least one hydrophilic ethylene monomer.

6. The silicone hydrogel contact lens as described in claim 5, wherein, The at least one hydrophilic ethylene monomer comprises: (1) alkyl (meth)acrylamides selected from the group consisting of: (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-3-methoxypropyl (meth)acrylamide, and combinations thereof; (2) hydroxyl-containing acrylic monomers selected from the group consisting of: N-2-hydroxyethyl (meth)acrylamide, N,N-bis(hydroxyethyl) (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N - Tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glyceryl methacrylate, di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (3) The following are carboxyl-containing acrylic monomers selected from the group consisting of: 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidovalerate, 4-(meth)acrylamidobutyric acid, 3-(meth)acrylamido-2-methylbutyric acid, 3-(meth)acrylamido-3-methylbutyric acid, 2-(meth)acrylamido-2-methyl-3,3-dimethylbutyric acid, 3-(meth)acrylamidohexanoic acid, 4-(meth)acrylamido-3,3-dimethylhexanoic acid, and combinations thereof; (4) The amino-containing acrylic monomers selected from the group consisting of: N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethylaminoethyl (meth)acrylamide, N-2-dimethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, N-3-dimethylaminopropyl (meth)acrylamide, 2-aminoethyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-ethylaminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate trimethylammonium hydrochloride, dimethylaminoethyl (meth)acrylate, and combinations thereof;(5) N-vinylamide monomers selected from the group consisting of: N-vinylpyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidone, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl -2-piperidinone, N-vinyl-3,5-dimethyl-2-piperidinone, N-vinyl-4,4-dimethyl-2-piperidinone, N-vinylcaprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof; (6) The following methylene-containing pyrrolidone monomers are selected from the group consisting of: 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof; (7) Acrylic monomers having C1-C4 alkoxyethoxy groups and selected from the group consisting of: ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4-alkoxy poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof;(8) Vinyl ether monomers selected from the group consisting of: ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof; (9) Allyl ether monomers selected from the group consisting of: ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and combinations thereof; (10) Ethylene monomers containing phosphorylcholine selected from the group consisting of: (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonium)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonium)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonium)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'- (trimethylammonium) ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonium) ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonium) ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonium) ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonium) ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonium) ethyl phosphate 2-((meth)acryloyloxy)propyl-2'-(trimethylammonium)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonium)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonium)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonium)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonium)ethyl phosphate, 2-(allyloxy)ethyl-2'- (trimethylammonium) ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonium) ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonium) ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonium) ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonium) ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonium) ethyl phosphate, and combinations thereof; (11) allyl alcohol;(12) N-2-hydroxyethyl vinylcarbamate; (13) N-carboxyvinyl-β-alanine (VINAL); (14) N-carboxyvinyl-α-alanine; (15) or combinations thereof.

7. The silicone hydrogel contact lens as described in claim 6, wherein, The at least one hydrophilic ethylene monomer includes N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or a combination thereof.

8. The silicone hydrogel contact lens as described in claim 6, wherein, The at least one hydrophilic ethylene monomer includes N,N-dimethyl (methyl)acrylamide.

9. The silicone hydrogel contact lens as described in claim 6, wherein, The at least one hydrophilic ethylene monomer includes N-2-hydroxyethyl (methyl)acrylamide, N,N-bis(hydroxyethyl) (methyl)acrylamide, N-3-hydroxypropyl (methyl)acrylamide, N-2-hydroxypropyl (methyl)acrylamide, N-2,3-dihydroxypropyl (methyl)acrylamide, N - Tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glyceryl methacrylate, di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, or combinations thereof.

10. The silicone hydrogel contact lens as described in claim 6, wherein, The crosslinked polymer material comprises repeating units of at least one non-silicone vinyl crosslinking agent.

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