Polysiloxane vinylic crosslinker with high refractive index

Abstract

The present invention provides a class of high RI polysiloxane vinylic crosslinkers. The polysiloxane vinylic crosslinkers of the invention each comprise (1) a polysiloxane segment comprising dimethylsiloxane units and aryl-containing siloxane units each having one methyl substituent and one organic substituent having up to 45 carbon atoms and at least one aryl moiety connected to the Si atom through a linking group having at least 2 (preferably 3) carbon atoms; and (2) an ethylenically unsaturated group. The invention also provides an insert or a silicone hydrogel contact lens comprising a crosslinked polymeric material comprising repeat units of at least one of such high RI polysiloxane vinylic crosslinkers.

Description

[0001] This invention relates to high refractive index (RI) polysiloxane ethylene crosslinkers—each having one or more aryl-containing siloxane units, each siloxane unit having a methyl substituent and an organic substituent having at least one aryl moiety connected to a Si atom via a flexible linker—and their use in the preparation of high RI inserts and high RI siloxane hydrogel contact lenses. Background Technology

[0002] In recent years, various inserts have been proposed for incorporating hydrogel contact lenses for various purposes (e.g., for corneal health, vision correction, diagnosis, etc.). See, for example, U.S. Patent Nos. 4,268,132, 4,401,371, 5,098,546, 5,156,726, 6,851,805, 7,490,936, 7,883,207, 8,154,804, 8,215,770, 8,348,424, 8,874,182, 9,176,332, 961,8773, 10,203,521, and 10,209,534; and U.S. Patent Application Publication No. 20,040,141,150. 20040212779, 2008 / 0208335, 2009 / 0091818, 20090244477, 2010 / 0072643, 2010 / 0076553, 20110157544, 2012 / 0120365, 2012 / 0140167, 2012 / 0234453, 2014 / 0276481 and 2015 / 0145155).

[0003] Inserts are typically made of non-hydrogel materials that do not absorb water, are non-water-swellable, and have low oxygen permeability and a relatively low refractive index. Inserts with high oxygen permeability are required to minimize adverse effects on corneal health. To impart higher optical performance to in-line contact lenses, such as diffractive multifocal optics, high refractive indices are desired. Inserts made of materials with high oxygen permeability and high refractive index are desirable. Summary of the Invention

[0004] In one aspect, the present invention provides a polysiloxane-ethylene crosslinking agent having a high refractive index (RI) and a relatively low glass transition temperature (Tg). The polysiloxane-ethylene crosslinking agent of the present invention comprises: a polysiloxane segment comprising a dimethylsiloxane unit, an aryl-containing siloxane unit (having a methyl substituent and an organic substituent having at least one aryl moiety connected to a Si atom via a linker having at least two (preferably three) carbon atoms); and an olefinic unsaturated group.

[0005] In another aspect, the present invention provides an insert made of a crosslinked polymer material comprising repeating units of a high-RI polysiloxane ethylene crosslinking agent of the present invention.

[0006] In another aspect, the present invention provides a siloxane hydrogel contact lens comprising a siloxane hydrogel bulk material comprising repeating units of the high-RI polysiloxane ethylene crosslinking agent of the present invention.

[0007] In another aspect, the present invention provides an embedded siloxane hydrogel contact lens comprising a siloxane hydrogel body material and an insert made of a crosslinked polymer material comprising units of the high-RI polysiloxane ethylene crosslinking agent of the present invention (described above) and embedded within the siloxane hydrogel body material.

[0008] 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. Attached Figure Description

[0009] Figure 1 The DSC diagram of the high-RI polysiloxane ethylene crosslinking agent of the present invention, obtained by using differential scanning calorimetry (DSC), is shown. 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] "Siloxane hydrogel contact lens" refers to a contact lens that contains siloxane hydrogel material as the body material (i.e., siloxane hydrogel 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] "Siloxane hydrogel" or "SiHy" can be used interchangeably to refer to a siloxane hydrogel comprising repeating units of at least one siloxane-containing monomer and / or a siloxane-containing vinyl crosslinking agent and at least one repeating unit of a hydrophilic vinyl monomer. It is typically formed by copolymerization of a polymerizable composition comprising at least one siloxane-containing monomer and / or a siloxane-containing vinyl crosslinking agent and at least one hydrophilic vinyl monomer.

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

[0017] "Embedded silicone hydrogel contact lens" refers to a silicone hydrogel contact lens that includes at least one insert made of a non-hydrogel material and embedded in a silicone hydrogel material that serves as the main lens material of the contact lens.

[0018] "Insertion" refers to any three-dimensional article made of a non-hydrogel material and having a size of at least 5 micrometers, but smaller, sufficient to be embedded in a silicone hydrogel contact lens. According to the invention, the non-hydrogel material can be any material capable of absorbing less than 5% (preferably about 4% or less, more preferably about 3% or less, even more preferably about 2% or less) of water by weight when fully hydrated.

[0019] According to the present invention, the thickness of the insert is less than the thickness of any embedded silicone hydrogel contact lens in the area where the insert is embedded. The insert can be any object having any geometry and can have any desired function. Preferred examples of inserts include, but are not limited to, thin rigid disks with curved surfaces for providing rigid central optics for masking astigmatism, such as rigid gas permeable (RGP) contact lenses, multifocal lens inserts, photochromic inserts, cosmetic inserts printed with color patterns thereon, etc.

[0020] As used in this article, "hydrophilic" describes a material or part thereof that will associate with water more readily than lipids.

[0021] "Ethylene monomers" refer to compounds that have a single, unique olefinic unsaturated group, are soluble in solvents, and can be polymerized by photochemical or thermal means.

[0022] 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.

[0023] 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.

[0024] 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 ), ethyleneoxycarbonylamino ( Where R o It is H or C1-C4 alkyl), ethyleneoxycarbonyloxy Vinylaminocarbonylamino ( Where R o It is H or C1-C4 alkyl), vinylaminocarbonyloxy Allyl, vinyl, styrene Or other groups containing C=C.

[0025] 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.

[0026] "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.

[0027] "(meth)acryloxy ((meth)acryloxy or (meth)acryloyloxy) monomer" refers to a monomer with a unique group. Ethylene monomers.

[0028] "(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).

[0029] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0030] The term "(meth)acrylate" refers to methacrylates and / or acrylates.

[0031] "N-vinylamide monomer" refers to an amide compound having a vinyl group (-CH=CH2) directly attached to a nitrogen atom of the amide group.

[0032] The term "enegroup" 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.

[0033] "Alkene monomers" refer to ethylene monomers that have a unique alkenyl group.

[0034] "Hydrophilic ethylene monomers" refer to ethylene monomers that typically produce water-soluble homopolymers or can absorb at least 10 percent by weight of water.

[0035] "Hydrophobic ethylene monomers" refer to ethylene monomers that typically produce homopolymers that are insoluble in water and can absorb less than 10% by weight of water.

[0036] 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.

[0037] Siloxanes, also commonly described as siloxanes, refer to molecules having at least one -Si-O-Si- moiety, where each Si atom carries two organic groups as substituents.

[0038] "Siloxane-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 wherein each Si atom carries at least two substituents (organic groups).

[0039] "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 the following groups is selected independently: 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-C18 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 linker -NR N1 - Amide linker -CONR N1 - Amide-CONR N1 R N1 ', a functional group consisting of a urethane linker -OCONH- and a C1-C4 alkoxy group, 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 up to 45 carbon atoms.

[0040] "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.

[0041] As used in this article, the term "fluid" indicates that a material is capable of flowing like a liquid.

[0042] 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.

[0043] 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.

[0044] "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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] The term "terminal olefinic unsaturated group" refers to an olefinic 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.

[0050] "Blended ethylene monomers" refers to ethylene monomers that can dissolve both the hydrophilic and hydrophobic components of a polymerizable composition to form a solution.

[0051] 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.

[0052] The term "post-curing surface treatment" for siloxane hydrogel bulk materials or SiHy contact lenses refers to the surface treatment process performed after SiHy lens preparations are formed into siloxane hydrogel bulk materials or SiHy contact lenses through curing (i.e., polymerization by thermal or photochemical means).

[0053] The terms “siloxane hydrogel lens preparation” or “SiHy lens preparation” can be used interchangeably to refer to a polymerizable composition comprising all the necessary polymerizable components known to those skilled in the art for the production of siloxane hydrogel (SiHy) contact lenses or SiHy lens body materials.

[0054] In general, the present invention relates to a class of high-RI polysiloxane ethylene crosslinking agents, each comprising (1) a polysiloxane segment comprising a dimethylsiloxane unit and an aryl-containing siloxane unit, each of the aryl-containing siloxane units having a methyl substituent and an organic substituent having up to 45 carbon atoms and at least one aryl moiety, the aryl moiety being connected to a Si atom via a linker having at least two (preferably at least three) carbon atoms; and (2) an olefinic unsaturated group.

[0055] There are some potential unique features associated with the use of the high-RI polysiloxane ethylene crosslinking agent of the present invention in the preparation of inserts or SiHy contact lenses with relatively high RI (refractive index).

[0056] First, the high-RI polysiloxane ethylene crosslinking agent of the present invention can be used to prepare inserts or SiHy contact lenses with high refractive index (RI 1.50) and relatively high oxygen permeability. Typically, polydimethylsiloxane has an RI value of 1.38-1.42. Such polydimethylsiloxane can be used to prepare inserts or SiHy contact lenses with relatively high oxygen permeability, but is not suitable for preparing inserts or SiHy contact lenses with high RI. In contrast, the high-RI polysiloxane ethylene crosslinking agent of the present invention contains an aryl moiety for imparting high RI, but also contains a dimethylsiloxane unit for imparting relatively high oxygen permeability to the resulting inserts or SiHy contact lenses. Inserts with high RI and high oxygen permeability can be used to prepare embedded diffractive multifocal siloxane hydrogel contact lenses. High-RI SiHy contact lenses can have a thinner thickness to achieve high oxygen permeability.

[0057] Secondly, in the high-RI polysiloxane ethylene crosslinking agent of the present invention, each aryl moiety is not directly connected to the Si atom in the siloxane unit, but is connected to the Si atom through a flexible linker. With this flexible linker, the aryl moiety can move more easily, and the high-RI polysiloxane ethylene crosslinking agent of the present invention can have a relatively low glass transition temperature (Tg). Inserts or lenses made of polysiloxanes with high Tg may be more brittle and more prone to cracking.

[0058] In one aspect, the present invention provides a high-RI polysiloxane ethylene crosslinking agent. The high-RI polysiloxane ethylene crosslinking agent of the present invention comprises: (1) a polysiloxane segment comprising a dimethylsiloxane unit and an aryl-containing siloxane unit, each of the aryl-containing siloxane units having a methyl substituent and an organic substituent having up to 45 carbon atoms and at least one aryl moiety, the aryl moiety being linked to a Si atom via a linker having at least 2 (preferably 3) carbon atoms; and (2) an olefinic unsaturated group (preferably (meth)acryloyl). The high-RI polysiloxane ethylene crosslinking agent of the present invention has an RI of at least 1.48 (preferably at least 1.51, more preferably at least 1.54, even more preferably 1.57) and a T of about 0°C or lower (preferably about -5.0°C or lower, more preferably about -10.0°C or lower, even more preferably about -20.0°C or lower). g .

[0059] In a preferred embodiment, the polysiloxane segment comprises at least 30 mol% (preferably at least 40 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol%, particularly preferably at least 70 mol%) of aryl-containing siloxane units.

[0060] In another preferred embodiment, the high-RI polysiloxane 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 100,000 Daltons, more preferably from 2,000 to 80,000 Daltons, and even more preferably from 2,500 to 60,000 Daltons).

[0061] According to the present invention, the high-RI polysiloxane ethylene crosslinking agent is preferably defined by formula (1).

[0062]

[0063] in:

[0064] υ1 is an integer from 1 to 400 (preferably from 3 to 350, more preferably from 5 to 300, and even more preferably from 10 to 250);

[0065] ω1 is an integer from 1 to 800 (preferably from 5 to 700, more preferably from 10 to 600, and even more preferably from 15 to 500);

[0066] E1 is Monovalent groups;

[0067] R0 is either hydrogen or methyl;

[0068] a1 is zero or 1;

[0069] X0 is either O or NR N1 ;

[0070] R N1 It is hydrogen or C1-C6 alkyl;

[0071] L0 is a C2-C8 alkylene divalent group, or -L0′-X1-L0″-. divalent groups;

[0072] L0' is a C2-C8 alkylene divalent group;

[0073] "L0" is a C3-C8 alkylene divalent group;

[0074] X1 is -O-, -NR N1 -、-NHCOO-、-OCONH-、-CONR N1 -or-NR N1 CO-;

[0075] q1 is an integer from 1 to 10;

[0076] AR stands for aryl;

[0077] L AR yes divalent groups;

[0078] L e It is -CH2-CH2-, -CH2-CHR0-R1-, -CH2-CHR0-R1-O-, -CH2-CHR0-R1-O-R2-, -C3H6-O-R2-, -C3H6-O-R2-O-, divalent groups;

[0079] a2 is zero, 1, or 2;

[0080] a3 is zero or 1;

[0081] R1 is a C1-C chain, whether straight or branched. 10 An alkylene divalent group, which may optionally be substituted with a C1-C4 alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an oxo group, or a combination thereof;

[0082] R2 is a C1-C chain, whether straight or branched. 10 alkylene divalent groups;

[0083] R3 is a C1-C4 alkylene divalent group that is either directly bonded, straight-chain, or branched;

[0084] X AR Each X2 is independently covalently bonded, a straight-chain or branched C1-C4 alkylene divalent group, or covalently linked with the following: -O-, -S-, -NR N2 -, -NHCOO-, -OCONH-, -NHCONR N2 -、-NR N2 CONH-、 -CONR N2 -、-NR N2 CO-、 -NHCOS-, -SCONH-, -COO-, or -OCO-;

[0085] R N2 It is hydrogen, straight-chain or branched C1-C6 alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted- or unsubstituted-phenyl-C1-C6 alkyl;

[0086] Each L x Independently, it is a straight-chain or branched C1-C4 chain, optionally having one or more hydroxyl groups or C1-C4-alkoxy or C1-C4-acylamino groups. 10 Alkyl divalent group, -CH2-CHOJ-CH2-O-R4-O-CH2-CHOH-CH2- Alternatively, it may have one or more hydroxyl or C1-C4-alkoxy groups and be a divalent group obtained by removing two hydrogen atoms from two different atoms of a hydrocarbon, said hydrocarbon having up to 20 carbon atoms and containing at least one divalent group selected from the group consisting of: cycloalkylene, substituted cycloalkylene, phenylene, substituted phenylene, heteroalkylene, and substituted heteroalkylene; and

[0087] Each of R4, R5, and R6 is independently a straight-chain or branched C1-C bond with zero or one hydroxyl group. 10 Alkylene divalent group.

[0088] In a preferred embodiment, in equation (1), a1 is zero and then E1 is Monovalent groups.

[0089] In another preferred embodiment, ω1 / (υ1+ω1) is from about 0.30 to about 0.95 (preferably from about 0.40 to about 0.90, more preferably from about 0.50 to about 0.90, and even more preferably from about 0.60 to about 0.85).

[0090] In another preferred embodiment, AR is phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracene, substituted anthracene, phenanthryl, or substituted phenanthryl.

[0091] In another preferred embodiment, AR is Monovalent groups, of which R7, R8, R9, and R 10 R 11 R 12 and R 13 They are independently of each other H, Cl, Br, F, CF3, CCl3, C1-C5 alkyl, C1-C5 alkoxy, C2-C5 acyloxy, OH, phenyl, phenoxy, benzyloxy, phenyl carbonyl, phenoxy carbonyl, phenyl carboxyl (phenyl carbonyloxy), or naphthyl.

[0092] The polysiloxane ethylene crosslinking agent of formula (1) can be prepared by a two-step or three-step method.

[0093] According to the two-step method, the polysiloxane containing hydrogen siloxane of formula (2) is obtained in the first step according to any known procedure.

[0094]

[0095] E1, υ1 and ω1 are defined as above for equation (1).

[0096] According to the two-step method, the hydrogen-containing siloxane polysiloxane of formula (2) 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 in the presence of a catalyst. By controlling the molar ratio of D4 to H4, the desired υ1 / ω1 value can be obtained. It should be understood that 1,3-bis(E1 group)-terminated tetramethyldisiloxanes can be prepared, for example, by reacting one of them with (meth)acryloyl chloride or vinyl isocyanate (or isopropenyl isocyanate).

[0097] In the second step of the two-step process, the hydrosiloxane of formula (2) can be reacted with an aryl olefin monomer (i.e., an olefin monomer containing phenyl, substituted phenyl, naphthyl or substituted naphthyl) in a platinum-catalyzed hydrosilanization reaction known to those skilled in the art to form the polysiloxane ethylene crosslinker of formula (1).

[0098] Any aryl-containing olefin monomer can be used to prepare polysiloxane ethylene crosslinking agents of formula (1), as long as the aryl-containing olefin monomer contains phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracene, substituted anthracene, phenanthrene, or substituted phenanthrene. Examples of such aryl-containing olefin monomers include, but are not limited to, vinylnaphthalene, vinylanthracene, vinylphenanthrene, vinylpyrene, vinyl biphenyl, vinyl terphenyl, vinylphenylnaphthalene, vinylphenylanthracene, vinylphenylphenanthrene, vinylphenylpyrene, vinylphenyl terphenyl, phenoxystyrene, phenylcarbonylstyrene, phenylcarboxystyrene, phenoxycarbonylstyrene, allylnaphthalene, allylanthracene, allylphenanthrene, allylpyrene, allyl biphenyl, allyl terphenyl, allylphenylnaphthalene, allylphenylanthracene, allylphenylphenanthrene, allylphenylpyrene, allylphenyl terphenyl, allylphenoxybenzene, allyl(phenylcarbonyl)benzene, allylphenoxybenzene, allyl(phenylcarbonyl)benzene, allyl(phenylcarboxy)benzene, allylphenyl ether, allyl benzyl ether, and allyl(phenoxycarbonyl)benzene.

[0099] Various aryl-containing olefin monomers can be obtained from commercial suppliers or prepared according to known methods. Preferred examples of aryl-containing olefin monomers include, but are not limited to, styrene, 2,5-dimethylstyrene, 2-(trifluoromethyl)styrene, 2-chlorostyrene, 3,4-dimethoxystyrene, 3-chlorostyrene, 3-bromostyrene, 3-vinylanisole, 3-methylstyrene, 4-bromostyrene, 4-tert-butylstyrene, 2,3,4,5,6-pentafluorostyrene, 2,4-dimethylstyrene, 1-methoxy-4-vinylbenzene, 1-chloro-4-vinylbenzene, 1-methyl-4-vinylbenzene, 1-(chloromethyl)-4-vinylbenzene, 1-(bromomethyl)-4-vinylbenzene, 3-nitrostyrene, 1,2-vinylphenylbenzene, 1,3-vinylphenylbenzene, 1,4-vinylphenylbenzene, 4-vinyl-1,1'-(4'-phenyl)biphenylene, 1-vinyl-4-(phenoxy)benzene, 1-vinyl-3-(phenoxy)benzene, 1-vinyl-2-(phenoxy)benzene, 1-vinyl 4-(phenylcarbonyl)benzene, 1-vinyl-3-(phenylcarboxyl)benzene, 1-vinyl-2-(phenoxycarbonyl)benzene, allyl phenyl ether, allyl benzyl ether, 2-biphenyl allyl ether, allyl 4-phenoxyphenyl ether, allyl 2,4,6-tribromophenyl ether, allyl phenyl carbonate, 1-allyloxy-2-trifluoromethylbenzene, allylbenzene, 1-phenyl-2-prop-2-enylbenzene, 4-phenyl-1-butene, 4-phenyl-1-butene 4-Alcohol, 1-(4-methylphenyl)-3-buten-1-ol, 1-(4-chlorophenyl)-3-buten-1-ol, 4-allyltoluene, 1-allyl-4-fluorobenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene, 1-allyl-3-methylbenzene, 2-allyl anisole, 4-allyl anisole, 1-allyl-4-(trifluoromethyl)benzene, allyl pentafluorobenzene, 1-allyl-2-methoxybenzene, 4-allyl-1,2-Dimethoxybenzene, 2-Allylphenol, 2-Allyl-6-methylphenol, 4-Allyl-2-methoxyphenol, 2-Allyloxyanisole, 4-Allyl-2-methoxyphenylacetate, 2-Allyl-6-methoxyphenol, 1-Allyl-2-bromobenzene, α-Vinylbenzyl alcohol, 1-Pheny-3-Buten-1-one, Allylbenzyl ether, (3-Allyloxy)propyl)benzene, Allylphenylethyl ether, 1-Benzyloxy-4-pentene, (1-Allyloxy)ethyl)benzene, 1-Phenylallylethyl ether, (2-Methyl-2-(2-Propylooxy)propyl)benzene, ((5-Hexenoxy)methyl)benzene, 1-Allyloxy-4-propoxybenzene, 1-Phenoxy-4-(3-Prop-2-enoxy) Propoxybenzene, 6-(4'-hydroxyphenoxy)-1-hexene, 4-but-3-enoxyphenol, 1-allyloxy-4-butoxybenzene, 1-allyloxy-4-ethoxybenzene, 1-allyl-4-benzyloxybenzene, 1-allyl-4-(phenoxy)benzene, 1-allyl-3-(phenoxy)benzene, 1-allyl-2-(phenoxy)benzene, 1-allyl-4-(phenylcarbonyl)benzene, 1-allyl-3-(phenylcarboxyl)benzene, 1-allyl-2-(phenoxycarbonyl)benzene, 1,2-allylphenylbenzene, 1,3-allylphenylbenzene, 1,4-allylphenylbenzene, 4-vinyl-1,1'-(4'-phenyl)biphenylene, 1-allyl-4-(phenoxy)benzene, 1-allyl-3 -(phenoxy)benzene, 1-allyl-2-(phenoxy)benzene, 1-allyl-4-(phenylcarbonyl)benzene, 1-allyl-3-(phenylcarboxyl)benzene and 1-allyl-2-(phenoxycarbonyl)benzene, 1-vinylnaphthyl, 2-vinylnaphthyl, 1-allylnaphthalene, 2-allylnaphthalene, allyl-2-naphthyl ether, 2-(2-methylprop-2-enyl)naphthalene, 2-prop-2-enylnaphthalene, 4-(2-naphthyl)-1-butene, 1-(3-butenyl)naphthalene, 1-allylnaphthalene, 2-allylnaphthalene, 1-allyl-4-naphthylnaphthalene, 2-(allyloxy)-1-bromonaphthalene, 2-bromo-6-allyloxynaphthalene, 1,2-vinyl(1-naphthyl)benzene, 1,2-vinyl(2-naphthyl)benzene, 1, 3-Vinyl(1-naphthyl)benzene, 1,3-Vinyl(2-naphthyl)benzene, 1,4-Vinyl(1-naphthyl)benzene, 1,4-Vinyl(2-naphthyl)benzene, 1-Naphthyl-4-vinylnaphthyl, 1-Allylnaphthyl, 2-Allylnaphthyl, 1,2-Allyl(1-naphthyl)benzene, 1,2-Allyl(2-naphthyl)benzene, 1,3-Allyl(1-naphthyl)benzene, 1,3-Allyl(2-naphthyl)benzene, 1,4-Allyl(1-naphthyl)benzene, 1,4-Allyl(2-naphthyl)benzene, 1-Allyl-4-naphthylnaphthyl, 1-Vinylanthracene, 2-Vinylanthracene, 9-Vinylanthracene, 1-Allylanthracene, 2-Allylanthracene, 9-Allylanthracene, 9-Pent-4-enylanthracene, 9-Allyl-1,2,3-4-Tetrachloroanthracene, 1-vinylphenanthrene, 2-vinylphenanthrene, 3-vinylphenanthrene, 4-vinylphenanthrene, 9-vinylphenanthrene, 1-allylphenanthrene, 2-allylphenanthrene, 3-allylphenanthrene, 4-allylphenanthrene, 9-allylphenanthrene, and combinations thereof.

[0100] According to the three-step method, the hydrogen-containing siloxane polysiloxane of the above formula (2) can be prepared according to the above procedure.

[0101] In the second step of the three-step method, the polysiloxane containing hydrogen siloxane of formula (2) is reacted with a first reactive functional group (E). e The olefin monomers are reacted in a platinum-catalyzed hydrosilylation reaction known to those skilled in the art to form a polysiloxane ethylene crosslinker having side-reactive functional groups as represented by formula (3).

[0102]

[0103] Where E1, υ1, ω1 and L e It is as defined above for equation (1) and E e The first reactive functional group is selected from the following groups: -COOH, -NHR N2 , -NCO, -OH, -SH, -CHO, epoxy groups and aziridine

[0104] Any olefin monomer can be used in the preparation of polysiloxane ethylene crosslinking agents of formula (3), provided that the olefin monomer contains reactive functional groups (-COOH, -NHR). N2 , -NCO, -OH, -SH, -CHO Various alkene monomers with reactive functional groups can be obtained from commercial suppliers or prepared according to known methods.

[0105] Examples of commercially available carboxyl-containing olefin monomers include, but are not limited to, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, and 6-heptenoic acid. Other examples include 2,2-dimethyl-4-pentanoic acid, 2-methyl-4-pentanoic acid, 2-propyl-4-pentanoic acid, 3-methyl-4-pentanoic acid, 4-vinylcyclohexanecarboxylic acid, 2-[4-(4-pentenyl)cyclohexyl]acetic acid, 4-propenylcyclohexanecarboxylic acid, 3-[2-(2-propenyl)cyclohexyl]propionic acid, 2-(4-vinylcyclohexyl)acetic acid, 4-[4-(2-propenyl)cyclohexyl]butyric acid, 2-vinylcyclohexyl-1-carboxylic acid, 2-,3- or 4-vinylbenzoic acid, 4-(2-propenyl)benzoic acid, 2-allylbenzoic acid, (4-vinylphenyl)acetic acid, and 2-methyl-2-(4-vinylphenyl)propionic acid.

[0106] Examples of commercially available alkene monomers having primary or secondary amino groups include, but are not limited to, allylamine, 3-butenylamine, 4-pentenylamine, 1,1-dimethylallylamine, 1-methyl-4-pentenylamine, 5-hexenylamine, 5-heptenylamine, 6-heptenylamine, N-ethyl-2-methylallylamine, N-ethylallylamine, N-allylmethylamine, N-allyl-1-pentylamine, N-allyl-2-methyl-1-pentylamine, N-allyl-2,3-dimethyl-1-pentylamine, N-allyl-1-hexylamine, N-allyl-2-methyl-1-hexylamine, and N-allyl-1-octylamine. N-Allyl-1-Decanamine, N-Allyl-1-Dodecaneamine, N-Allyl-1-Heptaneamine, N-Allyl-Ethylenediamine, N-Allyl-Cyclohexylamine, N-3-Butenylcyclohexylamine, N-4-Pentenylcyclohexylamine, N-5-Hexenylcyclohexylamine, 1-Amino-4-Vinyl-Cyclohexane, 1-Allyl-2,5-Dimethylpiperazine, 1-Allyl-piperazine, 4-Vinylaniline, N-Allylaniline, N-Allyl-Benzylamine, N-Allyl-α-Methylbenzylaniline, 4-Vinylpiperidine, 3-Vinylpiperidine, 2-Allylpyrrolidine, 3-Vinylpyrrolidine, etc.

[0107] Examples of commercially available alkene monomers having an isocyanate group include, but are not limited to, allyl isocyanate, 4-isocyanate-1-butene, 3-isocyanate-2-methyl-propene, 3-isocyanate-1-butene, 3-isocyanate-3-methyl-1-butene, 3-isocyanate-2,3-dimethyl-1-butene, 4-isocyanate-2-methyl-1-butene, 4-isocyanate-3,3-dimethyl-1-butene, 3-isocyanate-3-methyl-1-pentene, 4-isocyanate-4-methyl-1-pentene, 5-isocyanate-1-pentene, 3-isocyanate-1-hexene, 3-isocyanate-5,5-dimethyl-1-hexene, 1-isocyanate-2-heptene, etc.

[0108] 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 allyloxy. Ethanol, 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.

[0109] Examples of commercially available thiol-containing alkene monomers include, but are not limited to, allyl thiol, 3-buten-1-thiol, 3-methyl-3-buten-1-thiol, 2-methyl-3-buten-1-thiol, 2-methyl-3-buten-2-thiol, 4-penten-1-thiol, etc.

[0110] Examples of commercially available alkene monomers having aldehyde groups include, but are not limited to, 3-butenal, 4-pentanal, 5-hexenal, 2,2-dimethyl-4-pentenal, 2-methyl-4-pentenal, etc.

[0111] Examples of commercially available epoxide-containing olefin monomers include, but are not limited to, 3,4-epoxy-1-butene, 2-methyl-2-vinylethylene oxide, 3,4-epoxy-1-pentene, 4,5-epoxy-1-pentene, 1,2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene, 1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, allyloxy glycidyl ether, and 2-methyl-2-vinylethylene oxide, 4-vinyl-1-cyclohexene-1,2-epoxide, etc.

[0112] Examples of commercially available alkene monomers having an aziridine group include, but are not limited to, 2-vinylaziridine, 1-allylaziridine, N-allyl-2-methylaziridine, etc.

[0113] All of the commercially available alkene monomers described above can be used in this invention. Alternatively, alkene monomers having reactive functional groups can be prepared by reacting a compound having two alkenyl groups with a thiol having reactive functional groups (e.g., hydroxyl, primary amino, secondary amino, carboxyl, or ketone groups) based on a thiol-alkene "click" reaction as known in the art.

[0114] In the third step, the polysiloxane ethylene crosslinking agent of formula (3) is reacted with a crosslinking agent having the selectivity (-COOH, -NHR) N2 , -NCO, -OH, -SH, -CHO The second reactive functional group of the group (designated as "E") AR Aryl compounds of formula (1) are reacted under well-known coupling reaction conditions in the presence or absence of a coupling agent (i.e., having two of the reactive functional groups listed above) to form a high-RI polysiloxane ethylene crosslinker of formula (1).

[0115] For illustrative purposes, non-limiting examples of coupling reactions between a pair of matched co-reactive functional groups under various reaction conditions are given below, said co-reactive functional groups preferably selected from the group consisting of: primary group, secondary amino group, hydroxyl group, carboxyl group, acid anhydride group, aldehyde group, isocyanate group, epoxy group, aziridine group, acrylonitrile group, and mercapto group. Primary / secondary amine groups react with aldehyde or ketone groups to form Schiff bases, which can be further reduced to amine bonds; primary / secondary amine-NHR (where R is hydrogen or C1-C6 alkyl) react with acyl chloride or bromine groups or with acid anhydride groups to form amide linkages (-CO-NR-); amine-NHR reacts with N-hydroxysuccinimide ester groups to form amide linkages; amine-NHR reacts with carboxylic acid groups and N-hydroxysuccinimide in the presence of a coupling agent—a carbodiimide (e.g., 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-dicyclohexylcarbodiimide (DCC), 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide, or mixtures thereof) to form amide bonds; amine-NHR reacts with acrylonitrile groups (ring-opening) to form alkylene-diamidyl bonds (-CONH-CT1T2-(CH2)). p1-CONH-); amino-NHR reacts with isocyanate groups to form urea bonds (-NR-C(O)-NH-, where R is as defined above); amino-NHR reacts with epoxy groups or aziridine groups to form amine bonds (-C-NR-); hydroxyl groups react with isocyanates to form urethane linkages; hydroxyl groups react with epoxy groups or aziridines to form ether linkages (-O-); hydroxyl groups react with acyl chloride or bromine groups or with anhydride groups to form... Esterification linkages; carboxyl groups react with epoxy groups to form ester bonds; thiol groups (-SH) react with isocyanates to form thiocarbamate bonds (-NC(O)-S-); thiol groups react with epoxy groups or aziridines to form thioether bonds (-S-); thiol groups react with acyl chloride or bromine groups or with acid anhydride groups to form thioester bonds; thiol groups react with acrylonitrile groups in the presence of a catalyst to form bonds (-CONH-CT1T2-(CH2)). p1 -CO-S-); The thiol group reacts with the alkenyl or vinylsulfonyl group under thiol-alkene reaction conditions based on the thiol-alkene "click" reaction to form a thioether bond (-S-); The thiol group reacts with the (meth)acryloyl group under appropriate reaction conditions based on Michael addition to form a thioether bond.

[0116] The reaction conditions for the coupling reaction described above are taught in textbooks and are well known to those skilled in the art.

[0117] According to the present invention, coupling agents each having two reactive functional groups can be used in coupling reactions. Coupling agents having two reactive functional groups can be: diisocyanate compounds; diacyl halide compounds; dicarboxylic acid compounds; dicarboxylic acid anhydride compounds; diamine compounds; diol compounds; diepoxide compounds; diazacyclopropane compounds; diacyl lactone compounds; diene compounds; divinyl sulfone compounds; dimercapto compounds; thiolactone compounds; amino acid compounds; hydroxyl-containing amine compounds; amine compounds having one hydroxyl or ketone group; hydroxyl-containing carboxylic acid compounds; and thiols having a hydroxyl, carboxyl, or amino group.

[0118] For example, when E e and E PC When the groups are different or the same and selected from the group consisting of hydroxyl, primary amino, secondary amino, and thiol groups, diisocyanates, dicarboxylic acids (preferably dicarboxylic anhydrides), diazacyclopropanes, diepoxides, or diacyl lactones can be used for coupling E. e and E PC ; when E e and E PC When the groups are different or the same and selected from the group consisting of isocyanate, epoxy, aziridine, and carboxylic acid groups, diamines, dihydroxyl groups, dithiols, hydroxyl-containing amines, or hydroxyl-containing thiols can be used for coupling E. e and EPC ; when E e and E PC When both are carboxylic acid groups, biepoxides can be used for coupling E. e and E PC ; when E e and E PC When both are aldehyde groups, diamine compounds can be used to couple E. e and E PC ; when E e and E PC When both are thiol groups, divinyl sulfone compounds can be used for coupling E. e and E PC ; when E e and E PC When either of the amino groups is a primary or secondary amino group, thiolactone compounds can be used to covalently attach thiol groups to E via a bond. e and E PC either of them; when E PC When the group is an alkene or (meth)acryloyl group, thiols having hydroxyl, carboxyl, amino, or ketone groups can be used to covalently attach hydroxyl, carboxyl, amino, or ketone groups to the E group via bonds. PC Those skilled in the art are well aware of how to select one or more coupling agents to link E based on the selectivity and / or differential reactivity of a given functional group. e and E PC This forms the photochromic polysiloxane ethylene crosslinking agent of the present invention.

[0119] Commercially available dicarboxylic anhydrides include, but are not limited to, succinic anhydride, methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-dimethylsuccinic acid, glutaric anhydride, 3,3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3-methylglutaric anhydride, 3,3-tetramethylglutaric anhydride, diethylene glycol anhydride, adipic anhydride, etc.

[0120] Any suitable C3-C can be used in this invention. 24 Di-carboxylic acid compounds. Examples of preferred di-carboxylic acid compounds include, but are not limited to, straight-chain or branched C3-C compounds. 24 Aliphatic dicarboxylic acids, C5-C 24 Alicyclic or alicyclic-alicyclic dicarboxylic acids, C6-C 24Aromatic or aliphatic dicarboxylic acids, dicarboxylic acids containing amino or imino or N-heterocyclic compounds, and combinations thereof. Examples of suitable aliphatic dicarboxylic acids are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, dimethylmalonic acid, octadecylsuccinic acid, trimethyladipic acid, and dimer acids (dimers of unsaturated aliphatic carboxylic acids such as oleic acid). Examples of suitable alicyclic dicarboxylic acids are: 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxylic acid methylcyclohexane, and 4,4'-dicyclohexyldicarboxylic acid. Suitable examples of aromatic dicarboxylic acids are: terephthalic acid, isophthalic acid, phthalic acid, 1,3-, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenyl sulfone-dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl)-indene-manganese, 4,4'-diphenyl ether-dicarboxylic acid, and bis-p-(carboxyphenyl)-methane.

[0121] Any suitable diacyl halogen may be used in this invention. Examples of preferred diacyl halogens include, but are not limited to, fumarate chloride, octanoyl chloride, succinyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, sebacyl chloride, adipyl chloride, trimethyladipyl chloride, azeloyl chloride, dodecyl diacyl chloride, succinyl chloride, glutaryl chloride, oxaloyl chloride, dimer acyl chloride, and combinations thereof.

[0122] Any suitable diamine can be used in this invention. The organic diamine can be straight-chain or branched C2-C. 24 Aliphatic diamines, C5-C 24 Alicyclic or alicyclic-alicyclic diamines, or C6-C 24Aromatic or alkyl-aromatic diamines. Preferred organic diamines are N,N'-bis(hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, ethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N-methyl-1,3-diaminopropane, N-methylethylenediamine, N-ethylethylenediamine, N-isopropyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-butylethylenediamine, and 2,2-dimethyl-1,3-propanediamine. 1,4-Propanediamine, 1,5-Butanediamine, 1,5-Pentanediamine, Hexamethylenediamine, 2-Methyl-1,5-Pentanediamine, 1,6-Hexamethylenediamine, N,N'-Dimethyl-1,6-Hexamethylenediamine, 2,2,4(2,4,4)-Trimethyl-1,6-Hexanediamine, 1,3-Diamino-2-propanol, 1,2-Diaminoethane-1,2-diol, 1,1-Diaminoethane-1,2-diol, 1,4-Diaminodiamine 2,3-Butanediol, 1,3-Cyclopentanediamine, 1,4-Diaminocyclohexane, 1,3-Bis(aminomethyl)cyclohexane, 4,4′-Diaminodicyclohexylmethane, 4,4′-Methylenebis(2-methylcyclohexylamine), Isophorone diamine (3-aminomethyl-3,5,5-trimethylcyclohexylamine), m-Xylidene diamine, p-Xylidene diamine, Piperazine, 1-(2-aminoethyl)piperazine, 1,4- Bis(3-aminopropyl)piperazine, 2-piperazinylethylamine, 1-Boc-piperazine, 4-(2-aminoethyl)-1-Boc-piperazine, 1-(2-N-Boc-aminoethyl)piperazine, 4-(2-aminoethyl)-1-Boc-piperazine, 4-aminopiperidine, 3-aminopiperidine, 4-aminomethylpiperidine, 2-aminomethylpiperidine, 1-Boc-piperidine-4-carboxaldehyde, 1-Boc-piperidine-4-acetaldehyde, etc.

[0123] Any suitable C4-C can be used in this invention. 24 Diisocyanates. Examples of preferred diisocyanates include, but are not limited to, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 1,6-diisocyanate-2,2,4-trimethylhexane, octamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis-(4,4'-isocyanatomethyl)cyclohexane, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, toluene diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, etc.

[0124] Any suitable di-epoxy compound can be used in this invention. Preferred examples of diepoxy compounds are neopentyl glycol diglycidyl ether, 1,3-butadiene diepoxy, 1,4-butanediol diglycidyl ether, 1,2,7,8-diepoxyoctane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 1,6-hexanediol diglycidyl ether, and diglycerides. Glyceryl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bis[4-(glycidyloxy)phenyl]methane, bisphenol A diglycidyl ether (2,2-bis[4-(glycidyloxy)phenyl]propane), bisphenol A propoxylated diglycidyl ether, and combinations thereof.

[0125] Any suitable C2-C can be used in this invention. 24 Diols (i.e., compounds having two hydroxyl groups). Examples of preferred diols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol, various pentanediols, various hexanediols, various cyclohexanediols, 1,4-bis(2-hydroxyethyl)piperazine, bisphenol A, bisphenol F, 4,4'-methylenediphenol, and combinations thereof.

[0126] Any dithiol having 2 to 24 carbon atoms can be used in this invention to prepare the prepolymer of this invention. Examples of dithiols include, but are not limited to, C2-C4 dithiols. 12 Alkyl dithiols (e.g., ethyl dithiols, propyl dithiols, butyl dithiols, pentamethyl dithiols, hexamethylene dithiols, heptamethyl dithiols, octamethyl dithiols, nonamethylene dithiols, decamethyl dithiols), 3-ethylcyclohexane-1,2-dithiols, 3-(2-sulfonylethyl)cyclohexane-1-thiols, 3-(1-sulfonylethyl)cyclohexane-1-thiols, 2-methyl-5-(2-sulfonylpropyl)cyclohexane -1-Methylthiol, 2-propylcyclohexane-1,4-dithiol, benzene dithiol, methyl-substituted benzene dithiol, benzene dimethanethiol, 1,1-biphenyl-4,4'-dimethanethiol, biphenyl-4,4-dithiol, diethyl ether dithiol, triethylene glycol dithiol, tetraethylene glycol dithiol, dimercaprol, 2,3-dimercaptopropanol, dithiothreitol, etc.

[0127] Any amino acid may be used in this invention. Examples of amino acids include, but are not limited to, glycine, proline, alanine, valine, isoleucine, leucine, 2-aminoisobutyric acid, 4-aminobutyric acid, 3-aminoisobutyric acid, 3-amino-butyric acid, β-alanine, 1-amino-3-cyclopentanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, pyrrolidine-3-carboxylic acid, 4-piperidinecarboxylic acid, 3-piperidinecarboxylic acid, 1-piperazinacetic acid, etc.

[0128] Examples of compounds having an amino group and a hydroxyl or aldehyde (or ketone) group include, but are not limited to, 1-piperazine propanol, 2-[2-(1-piperazinyl)-ethoxy]-ethanol, 4-amino-1-piperazine ethanol, 4-piperidine methanol, 1-Boc-piperidine-4-carboxaldehyde, 4-formylpiperidine, N-Boc-4-piperidine acetaldehyde, etc.

[0129] Preferred examples of commercially available thiolactones include, but are not limited to, 4-butyryl thiolactone (or dihydro-2(3H)-thiophenone), 3-methyldihydro-2(3H)-thiophenone, 3-ethyldihydro-2(3H)-thiophenone, 3-(1-methylethyl)dihydro-2(3H)-thiophenone, 3,3-dimethyldihydro-2(3H)-thiophenone, 3-ethyl-3-methyldihydro-2(3H)-thiophenone, 3-acetyldihydro-2(3H)-thiophenone, N-acetyl homocysteine ​​thiolactone, N-propionyl homocysteine ​​thiolactone, N-butyryl homocysteine ​​thiolactone, and N-carboxybutyryl homocysteine ​​thiolactone (or 4-oxo-4-[(tetrahydro-2-oxo-3-thiophenyl)amino]-butyric acid).

[0130] Any divinyl sulfone compound may be used in this invention. Preferred examples of divinyl sulfone compounds include, but are not limited to, divinyl sulfone, bis(vinylsulfonyl)C1-C6 alkanes, 1,3-bis(vinylsulfonyl)-2-propanol, 1,1-bis(vinylsulfonyl)-1-propanol, 1,5-bis(vinylsulfonyl)-3-pentanol, 1,1-bis(vinylsulfonyl)-3-methoxypropane, 1,5-bis(vinylsulfonyl)-2,4-dimethylbenzene, and 1,4-bis(vinylsulfonyl)-2,3,5,6-tetrafluorobenzene.

[0131] Examples of preferred chain transfer agents containing primary and secondary amino groups include, but are not limited to, 2-mercaptoethylamine, 2-mercaptopropylamine, 3-mercaptopropylamine, 2-mercaptobutylamine, 3-mercaptobutylamine, 4-mercaptobutylamine, 5-mercaptopentylamine, 6-mercaptohexylamine, N-methylaminoethanethiol, N-ethylaminoethanethiol, N-methylaminopropanethiol, N-ethylaminopropanethiol, N-methylaminobutanethiol, N-ethylaminobutanethiol, 2-aminobenzylthiophenol, 3-aminobenzylthiophenol, 4-aminobenzylthiophenol, etc.

[0132] Examples of thiols having a carboxyl group include, but are not limited to, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, 2-methyl-3-sulfonylpropionic acid, 2-mercaptoisobutyric acid, 6-mercaptohexanoic acid, 8-mercaptooctanoic acid, 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptophenylacetic acid, 2-mercapto-2-phenylacetic acid, etc.

[0133] Preferred examples of hydroxyl-containing thiols include, but are not limited to, 2-mercaptoethanol, 3-mercaptopropanol, 1-mercapto-2-propanol, 2-mercapto-1-propanol, 4-mercapto-1-butanol, 2-mercapto-3-butanol, 3-mercapto-3-methyl-1-butanol, 4-mercapto-4-methyl-1-pentanol, 4-mercapto-4-methyl-2-pentanol, 6-mercapto-1-hexanol, 3-mercapto-1-hexanol, 8-mercapto-1-octanol, 9-mercapto-1-nonanol, 2-mercaptophenol, 3-mercaptophenol, 4-mercaptophenol, 2-mercaptobenzyl alcohol, 4-(6-mercaptohexoxy)benzyl alcohol, etc.

[0134] Examples of preferred thiols having a methyl carbonyl group (-COCH3) include, but are not limited to, 4-methyl-4-mercaptopentan-2-one, 3-mercapto-2-butanone, etc.

[0135] It is desirable to increase a first reactive functional group E by using one or more coupling agents (i.e., any of those mentioned above, etc.). e With the second functional group E of aryl compounds AR The length of the covalent connection between and / or E e and E AR One of them is transformed into a different reactive functional group that will react with another group (e.g., in the case where a3 is an integer from 1 to 2 in the above formula (1)).

[0136] Any aryl compound can be used to prepare the high-RI polysiloxane ethylene crosslinking agent of the present invention, as long as they contain reactive functional groups, such as hydroxyl, carboxyl, primary amino, secondary amino, isocyanate, epoxy, aziridine, thiol, ketone, or olefinic unsaturated groups (e.g., alkenyl, vinyl, vinylsulfonyl, acryloyl, and methacryloyl).

[0137] Various reactive aryl compounds can be obtained from commercial sources or prepared by following procedures known to those skilled in the art, including those described in patents and literature.

[0138] The high-RI polysiloxane vinyl crosslinking agents of the present invention (especially those of formula (1) as defined above) can be particularly used to prepare hydrophobic crosslinked polymer materials for forming high-RI inserts and siloxane hydrogel polymer materials for forming siloxane hydrogel contact lenses having high RI and high Dk (oxygen permeability), which is another aspect of the present invention. Those skilled in the art know how to prepare hydrophobic crosslinked polymer materials or siloxane hydrogel materials from polymerizable compositions according to any known polymerization mechanism.

[0139] In another aspect, the present invention provides an insert made of a hydrophobic crosslinked polymer material comprising repeating units of the high-RI polysiloxane ethylene crosslinking agent of the present invention (as described above).

[0140] In another aspect, the present invention provides a siloxane hydrogel contact lens comprising a crosslinked polymer material, the crosslinked polymer material comprising: units of the polysiloxane ethylene crosslinking agent of the present invention (as described above).

[0141] According to the present invention, the inserts or siloxane hydrogel (SiHy) contact lenses 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 manufacture inserts or SiHy contact lenses. For example, inserts or SiHy contact lenses can be produced by conventional "rotational molding" as described, for example, in US 3408429, or by a fully cast molding method as described in US Patent Nos. 4347198; 5508317; 5583463; 5789464; and 5849810, in a static form, or by lathe-like cutting of polymeric material buttons used in the preparation of custom contact lenses. In casting molding, a polymerizable composition (i.e., the insert preparation or SiHy lens preparation) is typically dispensed into a mold and thermally or photocured (i.e., polymerized and / or crosslinked) in the mold used to prepare the insert or SiHy contact lens.

[0142] Lens molds for preparing inserts or 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 comprises at least two mold sections (or portions) or half-molds, namely a first half-mold and a second half-mold. 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 an insert-forming cavity or 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.

[0143] Methods for preparing mold areas for casting contact lenses or inserts are generally well known to those skilled in the art. The methods of this invention are not limited to any particular method of mold formation. In fact, any method of mold formation can be used in this 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 the half-molds are disclosed in U.S. Patent Nos. 4,444,711; 4,460,534; 5,843,346; and 5,894,002.

[0144] Almost all materials known in the art for mold making can be used to make molds for making contact lenses or inserts. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, and PMMA can be used. COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene from TiconagmbH, Frankfurt, Germany and Summit, New Jersey), etc. Other materials that allow UV light transmission, such as quartz glass and sapphire, can be used.

[0145] The insert formulation (i.e., polymerizable composition) used to prepare the inserts of the present invention comprises a high-RI polysiloxane vinyl crosslinking agent, other copolymerizable components, a free radical initiator (thermal initiator or photoinitiator) (any of those described below), optionally a UV-absorbing vinyl monomer (any of those described below), optionally a UV / high-energy ultraviolet (“HEVL”) absorbing vinyl monomer, optionally a photochromic vinyl monomer, etc., as known to those skilled in the art.

[0146] Examples of copolymerizable components for use in insert formulations include, but are not limited to, hydrophobic acrylic monomers (any of those described below), aryl vinyl monomers (any of those described below), hydrophobic vinyl monomers other than hydrophobic acrylic monomers (any of those described below), and vinyl crosslinkers (any of those described below).

[0147] The SiHy lens formulation (i.e., polymerizable composition) used to prepare the SiHy contact lens of the present invention comprises a high-RI polysiloxane vinyl crosslinking agent, other copolymerizable components, a free radical initiator (thermal initiator or photoinitiator) (any of those described below), optionally a UV-absorbing vinyl monomer (any of those described below), optionally a UV / HEVL-absorbing vinyl monomer, optionally a photochromic vinyl monomer, etc., as known to those skilled in the art. Various siloxane hydrogel lens formulations have been described in numerous patents and patent applications published up to the filing date of this application and have been used in the production of commercial SiHy contact lenses. Examples of commercial SiHy contact lenses include, but are not limited to, asmofilcon A, balafilcon A, comfilcon A, delefilcon A, efrofilcon A, enfilcon A, fanfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, smafilcon A, somofilcon A, and stenfilcon A. These can be used in the lens forming compositions of the present invention.

[0148] Examples of copolymerizable components used in SiHy lens fittings include, but are not limited to, (1) at least one siloxane-containing ethylene monomer (any of those described below) and / or at least one siloxane-containing ethylene crosslinking agent (any of those described below); (2) at least one hydrophilic ethylene monomer (any of those described below); (3) optionally at least one hydrophobic nonsiloxane ethylene monomer (any of those described below); and (4) optionally at least one nonsiloxane ethylene crosslinking agent (any of those described below).

[0149] Any hydrophobic acrylic monomer can be used to form the inserts of the present invention. Examples of hydrophobic acrylic monomers include siloxane-containing acrylic monomers (any of those described above in this application), non-siloxane hydrophobic acrylic monomers (any of those described above in this application), fluorine-containing acrylic monomers (any of those described above in this application), aryl acrylic monomers (any of those described below), and combinations thereof.

[0150] Examples of aryl acrylate monomers include, but are not limited to: 2-ethylphenoxy acrylate; 2-ethylphenoxy methacrylate; phenyl acrylate; phenyl methacrylate; benzyl acrylate; benzyl methacrylate; 2-phenylethyl acrylate; 2-phenylethyl methacrylate; 3-phenylpropyl acrylate; 3-phenylpropyl methacrylate; 4-phenylbutyl acrylate; 4-phenylbutyl methacrylate; 4-methylphenyl acrylate; 4-methylphenyl methacrylate; 4-methylbenzyl acrylate; 4-methylbenzyl methacrylate; 2-(2-methylphenyl)ethyl acrylate ; 2-(2-methylphenyl)ethyl methacrylate; 2-(3-methylphenyl)ethyl methacrylate; 2-(3-methylphenyl)ethyl methacrylate; 2-(4-methylphenyl)ethyl methacrylate; 2-(4-methylphenyl)ethyl methacrylate; 2-(4-propylphenyl)ethyl methacrylate; 2-(4-propylphenyl)ethyl methacrylate; 2-(4-(1-methylethyl)phenyl)ethyl methacrylate; 2-(4-(1-methylethyl)phenyl)ethyl methacrylate; 2-(4-methoxyphenyl)ethyl methacrylate; 2-(4-methoxyphenyl)ethyl methacrylate 2-(4-cyclohexylphenyl)ethyl acrylate; 2-(4-cyclohexylphenyl)ethyl methacrylate; 2-(2-chlorophenyl)ethyl acrylate; 2-(2-chlorophenyl)ethyl methacrylate; 2-(3-chlorophenyl)ethyl acrylate; 2-(3-chlorophenyl)ethyl methacrylate; 2-(4-chlorophenyl)ethyl methacrylate; 2-(4-chlorophenyl)ethyl methacrylate; 2-(4-bromophenyl)ethyl acrylate; 2-(4-bromophenyl)ethyl methacrylate; 2-(3-phenylphenyl)ethyl methacrylate; 2-(3-phenylphenyl)ethyl methacrylate 2-(4-phenylphenyl)ethyl acrylate; 2-(4-phenylphenyl)ethyl methacrylate; 2-(4-benzylphenyl)ethyl acrylate; 2-(4-benzylphenyl)ethyl methacrylate; 2-(phenylthio)ethyl acrylate; 2-(phenylthio)ethyl methacrylate; 2-benzyloxyethyl acrylate; 3-benzyloxypropyl acrylate; 2-benzyloxyethyl methacrylate; 3-benzyloxypropyl methacrylate; 2-[2-(benzyloxy)ethoxy]ethyl acrylate; 2-[2-(benzyloxy)ethoxy]ethyl methacrylate; or combinations thereof. More preferably, hydrophobic acrylic monomers are 2-phenylethyl acrylate; 3-phenylpropyl acrylate; 4-phenylbutyl acrylate; 5-phenylpentyl acrylate; 2-benzyloxyethyl acrylate; 3-benzyloxypropyl acrylate; 2-[2-(benzyloxy)ethoxy]ethyl acrylate; and their corresponding methacrylates. The arylacrylate monomers listed above are available from commercial sources or can alternatively be prepared according to methods known in the art.

[0151] Examples of hydrophobic monomers other than hydrophobic acrylic monomers include vinyl alkyl esters (any of those described above in this application), vinyloxyalkanes (any of those described above in this application), and combinations thereof.

[0152] Preferred examples of hydrophobic nonsiloxane vinyl monomers may be nonsiloxane hydrophobic acrylic monomers ((meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, cyclohexyl methacrylate, (meth)acrylate, 2-ethylhexyl methacrylate, (meth)acrylate, isobornyl methacrylate, (meth)acrylonitrile, or combinations thereof), and fluorinated acrylic monomers (e.g., perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, perfluoro-substituted -C2-C of (meth)acrylate described below). 12 Alkyl esters, vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, etc.), vinyloxyalkanes (e.g., vinyl ethyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, etc.), styrene, vinyltoluene, vinyl chloride, vinylidene chloride, 1-butene, and combinations thereof.

[0153] In this invention, any suitable perfluoro-substituted -C2-C of (meth)acrylic acid can be used. 12 Alkyl esters. Perfluoro-substituted (meth)acrylic acid with -C2-C esters. 12 Examples of alkyl esters include, but are not limited to, 2,2,2-trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, heptafluorobutyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, pentafluorophenyl (meth)acrylate, and combinations thereof.

[0154] Any suitable vinyl crosslinking agent can be used to prepare the inserts of the present invention. Examples of preferred vinyl crosslinking agents include, but are not limited to: polysiloxane vinyl crosslinking agents (any of those described below) and / or non-siloxane vinyl crosslinking agents.

[0155] Examples of non-siloxane vinyl crosslinking agents include, but are not limited to, acrylic crosslinking agents (any of those described below), aryl crosslinking agents (e.g., divinylbenzene, 2-methyl-1,4-divinylbenzene, bis(4-vinylphenyl)methane, 1,2-bis(4-vinylphenyl)ethane, etc.), tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, and combinations thereof.

[0156] Examples of acrylic crosslinking agents include, but are not limited to, ethylene glycol di(meth)acrylate; 1,3-propanediol di(meth)acrylate; 2,3-propanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; glycerol 1,3-diglyceryl alcohol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate; and others. Di(meth)acrylate of alcohol; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; ethylene bis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate; bis[2-(meth)acryloyloxyethyl]phosphate; 3,4-bis[(meth)acryloyl]tetrahydrofuran; di(meth)acrylamide; 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'-Hexamethylenebis(meth)acrylamide; N,N'-Dihydroxyethylenebis(meth)acrylamide; N,N'-Propylenebis(meth)acrylamide; N,N'-2-Hydroxypropylidenebis(meth)acrylamide; N,N'-2,3-Dihydroxybutylidenebis(meth)acrylamide; 1,3-Bis( Methacrylamide propane-2-yl phosphate dihydrogen ester; piperazine diacrylamide; pentaerythritol tri(meth)acrylate; trimethylolpropane tri(meth)acrylate; tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; 1,3,5-tri(meth)acryloylhexahydro-1,3,5-triazine; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane)tetra(meth)acrylate; bisphenol A di(meth)acrylate; or combinations thereof.

[0157] According to the present invention, the siloxane-containing ethylene monomer can be any siloxane-containing ethylene monomer known to those skilled in the art. Preferred examples of siloxane-containing ethylene monomers include, but are not limited to, ethylene monomers each having a bis(trialkylsiloxy)alkylsilyl or tri(trialkylsiloxy)silyl group, polysiloxane ethylene monomers, 3-methacryloyloxypropylpentamethyldisiloxane, tert-butyldimethyl-siloxane ethyl vinyl carbonate, trimethylsilyl ethyl vinyl carbonate, and trimethylsilyl methyl vinyl carbonate, and combinations thereof.

[0158] Preferred polysiloxane vinyl monomers can be obtained from commercial suppliers (e.g., Shin-Etsu, Gelest, etc.); prepared according to the operating steps 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 subjecting (meth)acrylate or (meth)acrylamide or (meth)acrylate to a process. It can be prepared by reacting acryloyloxy polyethylene glycol with mono-glycidoxypropyl-terminated polydimethylsiloxane; by reacting glycidyl (meth)acrylate with mono-methanol-terminated polydimethylsiloxane, mono-aminopropyl-terminated polydimethylsiloxane, or mono-ethylaminopropyl-terminated polydimethylsiloxane; or by reacting isocyanate (meth)acrylate with mono-methanol-terminated polydimethylsiloxane according to a coupling reaction well known to those skilled in the art.

[0159] Preferred ethylene monomers of siloxanes, each having a bis(trialkylsiloxy)silyl or tri(trialkylsiloxy)silyl group, can be prepared according to the procedures described in U.S. Patent Nos. 5070215, 6166236, 7214809, 8475529, 8658748, 9097840, 9103965, and 9475827.

[0160] 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 macromonomer A, macromonomer B, macromonomer C, and macromonomer D as described in 5,760,100; 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 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.

[0161] A preferred class of polysiloxane-ethylene crosslinking agents is di(meth)acryloyloxy-terminated polysiloxane-ethylene crosslinking agents, 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), which can be prepared according to the procedure disclosed in US Patent No. 10081697.

[0162] Another preferred class of polysiloxane ethylene crosslinking agents are the following ethylene crosslinking agents, each comprising a unique polysiloxane segment and two terminal (meth)acryloyl groups, which are available from commercial suppliers; prepared by reacting (meth)acryloyl chloride (glycidyl methacrylate) with di-amino-terminated polydimethylsiloxane or di-hydroxy-terminated polydimethylsiloxane; prepared by reacting ethyl isocyanate (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.

[0163] Other preferred types of polysiloxane ethylene crosslinking agents are extended-chain polysiloxane ethylene crosslinking agents, each having at least two polysiloxane segments connected by a linker between each pair of polysiloxane 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.

[0164] 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), allyl alcohol, N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-propane (VINAL), N-carboxyvinyl-α-propane, and combinations thereof.

[0165] Examples of alkyl (meth)acrylamides include, but are not limited to, (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.

[0166] Examples of hydroxyl-containing acrylic monomers include, but are not limited to, 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, and combinations thereof.

[0167] Examples of carboxyl-containing acrylic monomers include, but are not limited to, 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamido-propionic 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.

[0168] Examples of amino-containing acrylic monomers include, but are not limited to, 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, trimethylammonium 2-hydroxypropyl(meth)acrylate hydrochloride, dimethylaminoethyl(meth)acrylate, and combinations thereof.

[0169] Examples of N-vinylamide monomers include, but are not limited to, 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-vinylpiperidone (also known as N-vinyl-2-piperidone), 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... Alkenyl-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.

[0170] Examples of methylene-containing pyrrolidone monomers include, but are not limited to, 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.

[0171] Examples of acrylic monomers having C1-C4 alkoxyethoxy groups include, but are not limited to, ethylene glycol methyl ether (meth)acrylates, di(ethylene glycol) methyl ether (meth)acrylates, tri(ethylene glycol) methyl ether (meth)acrylates, tetra(ethylene glycol) methyl ether (meth)acrylates, C1-C4-alkoxy poly(ethylene glycol) (meth)acrylates 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.

[0172] Examples of vinyl ether monomers include, but are not limited to, 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.

[0173] Examples of allyl ether monomers include, but are not limited to, 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.

[0174] Examples of ethylene monomers containing phosphorylcholine include, but are not limited to, (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.

[0175] Any suitable UV-absorbing vinyl monomer and UV / HEVL-absorbing vinyl monomer can be used in the polymerizable compositions used to prepare the preformed SiHy contact lenses of the present invention. Examples of preferred UV-absorbing vinyl monomers and UV / HEVL-absorbing vinyl monomers include, but are not limited to: 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acryloyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamidomethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloyloxypropyl-3'-... 2-(2'-hydroxy-5'-methacryloyloxypropylphenyl)benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-1), 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-5), 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL- 2) 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate Acrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol (WL-8), 2-{2'-hydroxy-3'-tert-5'[3”-(4”-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-vinyl-(UVAM), 2-[2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)]-2H-benzotriazole (2-acrylic acid, 2-methyl-,2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl ester (Norbloc), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl] 2-(2'-hydroxy-5'-methacrylamide-5'-benzotriazole (UV23), 2-(2'-hydroxy-5'-methacrylamide-5'-benzotriazole (UV6), 2-(3-allyl-2-hydroxy-5'-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-methylallyl-5'-methylphenyl)-2H-benzotriazole (UV12), 2-3'-tert-butyl-2'-hydroxy-5'-(3'-dimethylvinylsilylpropoxy)-2'-hydroxy-5'-methoxy-5'-benzotriazole (UV15), 2-(2'-hydroxy-5'-methacrylamide-3'-tert-butyl-2'-benzotriazole (UV15), 2-(2'-hydroxy-5'-methacrylamide-5'-benzotriazole)-5'-methoxy-2'-benzotriazole (UV12), 2-3'-tert-butyl-2'-hydroxy-5'-(3'-dimethylvinylsilylpropoxy)-2'-hydroxy-5'-benzotriazole (UV15), 2-(2'-hydroxy-5'-methacrylamide-3'-tert-butyl-5'-benzotriazole)-5'-methoxy-2'-benzotriazole (UV15), 2-(2'-hydroxy-5'-methacrylamide-5'-benzotriazole)-5'-methoxy-2'-benzotriazole (UV12), 2-(2'-hydroxy-5'-methacrylamide-5'-methacrylamide-5'-benzotriazole)-5'-benzotriazole (UV15), 2-(2'-hydroxy-5'-methacrylamide-5'-benzotriazole)-5'-methoxy-2'-benzotriazole (UV12), 2-(2'-hydroxy-5'-methacrylamide-5'-methacryl H-benzotriazole (UV16), 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV16A), 3-[3-tert-butyl-5-(5-chlorobenzotriazole-2-yl)-4-hydroxyphenyl]-propyl 2-methacrylate (16-100, CAS#96478-15-8), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazole-2-yl)phenoxy)ethyl methacrylate (16-102); phenol, 2-(5-chloro-2H-benzotriazole-2-yl)-6-methoxy-4-(2- Propylene-1-yl (CAS#1260141-20-5); 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole; phenol, 2-(5-vinyl-2H-benzotriazole-2-yl)-4-methyl-, homopolymer (9CI) (CAS#83063-87-0). According to the invention, the polymerizable composition comprises one or more UV-absorbing vinyl monomers in an amount of about 0.1 wt% to about 3.0 wt%, preferably about 0.2 wt% to about 2.5 wt%, more preferably about 0.3 wt% to about 2.0 wt% relative to all polymerizable components in the polymerizable composition.

[0176] Examples of preferred photochromic ethylene monomers include polymerizable naphthopyran, polymerizable benzopyran, polymerizable indenenaphthopyran, polymerizable phenanthrenepyran, polymerizable spiro(benzoindoline)-naphthopyran, polymerizable spiro(indoline)benzopyran, polymerizable spiro(indoline)-naphthopyran, polymerizable spiro(indoline)quinopyran, polymerizable spiro(indoline)-pyran, polymerizable naphthooxazine, polymerizable spirobenzopyran; polymerizable spirobenzopyran, polymerizable spirobenzothiaran, polymerizable naphthonaphthione, polymerizable spirooxazine, polymerizable spiro(indoline)naphthooxazine, polymerizable spiro(indoline)pyridinobenzooxazine, polymerizable spiro(benzoindoline)pyridinobenzoxazine, polymerizable spiro(benzoindoline)pyran The following are polymerizable compounds: pyridobenzoxazine, polymerizable spiro(benzoindoline)naphthooxazine, polymerizable spiro(indoline)-benzoxazine, polymerizable diarylethylene, and combinations thereof, as disclosed in U.S. Patent Nos. 4,929,693, 5,166,345, 6,017,121, 7,556,750, 7,584,630, 7,999,989, 8,158,037, 8,697,770, 8,741,188, 9,052,438, 9,097,916, 9,465,234, 9904,074, 10,197,707, 601,9914, 6,113,814, 6,149,841, 6,296,785, and 6,348,604.

[0177] 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).

[0178] 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-trimethylbenzoyldiphenylphosphine 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 formulations for preparing SiHy contact lenses contain 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.

[0179] The polymerizable composition (insertion formulation or SiHy lens formulation) 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.

[0180] Solvent-free polymerizable compositions typically contain at least one blended ethylene monomer as a reactive solvent for dissolving all other polymerizable components of solvent-free SiHy lens preparations.

[0181] Preferred examples of blended ethylene monomers include, but are not limited to, (meth)acrylic acid C1-C 10 Alkyl esters, cyclopentyl acrylates, cyclohexyl methacrylates, cyclohexyl acrylates, isobornyl methacrylate, styrene, 4,6-trimethylstyrene (TMS), tert-butylstyrene (TBS), trifluoroethyl methacrylate, hexafluoro-isopropyl methacrylate, hexafluorobutyl methacrylate, or combinations thereof. Preferably, methyl methacrylate is used as a blending vinyl monomer in the preparation of solvent-free SiHy lens formulations.

[0182] 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.

[0183] According to the present invention, a polymerizable composition (insertion article or SiHy lens article) can be introduced (dispensed) into a cavity formed by the male and female halves of a mold according to any known method.

[0184] After the polymerizable composition is dispensed into a mold, it is polymerized to produce SiHy contact lenses. As is known to those skilled in the art, crosslinking can be initiated thermally or photochemically.

[0185] The thermal polymerization is suitably 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 within a wide range, but is suitably, 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, for example, nitrogen or argon.

[0186] 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.

[0187] This allows the molded insert or SiHy contact lens to be removed from the mold, and the mold opening can occur in a manner known per se.

[0188] A liquid extraction medium can be used to extract molded inserts or SiHy contact lenses 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 in 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.

[0189] After extraction, the siloxane 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.

[0190] Hydrated siloxane hydrogel contact lenses can be further subjected to other processes, such as surface treatment, encapsulation in lens packaging with packaging solutions 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.

[0191] 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, wherein the base includes a cavity for receiving a sterile packaging solution and the contact lens.

[0192] 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.

[0193] 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:

[0194] 1. A polysiloxane-ethylene crosslinking agent, comprising:

[0195] (1) A polysiloxane segment comprising a dimethylsiloxane unit and an aryl-containing siloxane unit, the aryl-containing siloxane unit having a methyl substituent and an organic substituent having up to 45 carbon atoms and at least one aryl moiety, the aryl moiety being connected to a Si atom via a linker having at least two (preferably at least three) carbon atoms; and

[0196] (2) Alkenyl bond unsaturated groups.

[0197] 2. The polysiloxane ethylene crosslinking agent as described in embodiment 1, wherein the polysiloxane ethylene crosslinking agent has a refractive index of at least 1.48 and a To of about 0°C or lower. g .

[0198] 3. The polysiloxane ethylene crosslinking agent as described in embodiment 2, wherein the polysiloxane ethylene crosslinking agent has a refractive index of at least 1.51.

[0199] 4. The polysiloxane ethylene crosslinking agent as described in embodiment 2, wherein the polysiloxane ethylene crosslinking agent has a refractive index of at least 1.54.

[0200] 5. The polysiloxane ethylene crosslinking agent as described in embodiment 2, wherein the polysiloxane ethylene crosslinking agent has a refractive index of at least 1.57.

[0201] 6. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane ethylene crosslinking agent has a Tc of about -5.0°C or lower. g .

[0202] 7. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane ethylene crosslinking agent has a Tc of about -10.0°C or lower. g .

[0203] 8. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane ethylene crosslinking agent has a Tc of about -20.0°C or lower. g .

[0204] 9. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane segment comprises at least 30 mol% of the aryl-containing siloxane unit.

[0205] 10. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane segment comprises at least 40 mol% of the aryl-containing siloxane unit.

[0206] 11. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane segment comprises at least 50 mol% of the aryl-containing siloxane unit.

[0207] 12. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane segment comprises at least 60 mol% of the aryl-containing siloxane unit.

[0208] 13. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 5, wherein the polysiloxane segment comprises at least 70 mol% of the aryl-containing siloxane unit.

[0209] 14. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 13, wherein the polysiloxane ethylene crosslinking agent has a number average molecular weight of at least 1000 Daltons.

[0210] 15. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 14, wherein the polysiloxane ethylene crosslinking agent has a number average molecular weight from about 1,500 Daltons to about 100,000 Daltons.

[0211] 16. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 14, wherein the polysiloxane ethylene crosslinking agent has a number average molecular weight from 2,000 Daltons to 80,000 Daltons.

[0212] 17. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 14, wherein the polysiloxane ethylene crosslinking agent has a number average molecular weight from 2,500 to 60,000 Daltons.

[0213] 18. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 17, wherein the polysiloxane ethylene crosslinking agent is defined by formula (1).

[0214]

[0215] in:

[0216] υ1 is an integer from 1 to 400;

[0217] ω1 is an integer from 1 to 800;

[0218] E1 is Monovalent groups;

[0219] R0 is either hydrogen or methyl;

[0220] a1 is zero or 1;

[0221] X0 is either O or NR N1 ;

[0222] R N1 It is hydrogen or C1-C6 alkyl;

[0223] L0 is a C2-C8 alkylene divalent group, or -L0′-X1-L0″-. divalent groups;

[0224] L0' is a C2-C8 alkylene divalent group;

[0225] "L0" is a C3-C8 alkylene divalent group;

[0226] X1 is -O-, -NR N1 -、-NHCOO-、-OCONH-、-CONR N1 -or-NR N1 CO-;

[0227] q1 is an integer from 1 to 10;

[0228] AR stands for aryl;

[0229] L AR yes divalent groups;

[0230] L e It is -CH2-CH2-, -CH2-CHR0-R1-, -CH2-CHR0-R1-O-, -CH2-CHR0-R1-O-R2-, -C3H6-O-R2-, -C3H6-O-R2-O-, divalent groups;

[0231] a2 is zero, 1, or 2;

[0232] a3 is zero or 1;

[0233] R1 is a C1-C chain, whether straight or branched. 10 An alkylene divalent group, which may optionally be substituted with a C1-C4 alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an oxo group, or a combination thereof;

[0234] R2 is a C1-C chain, whether straight or branched. 10 alkylene divalent groups;

[0235] R3 is a C1-C4 alkylene divalent group that is either directly bonded, straight-chain, or branched;

[0236] X AR Each X2 is independently covalently bonded, a straight-chain or branched C1-C4 alkylene divalent group, or covalently linked with the following: -O-, -S-, -NR N2 -, -NHCOO-, -OCONH-, -NHCONR N2 -、-NR N2 CONH-、 -CONR N2 -、-NR N2 CO-、 -NHCOS-, -SCONH-, -COO-, or -OCO-;

[0237] R N2 It is hydrogen, straight-chain or branched C1-C6 alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted- or unsubstituted-phenyl-C1-C6 alkyl;

[0238] Each L x Independently, it is a straight-chain or branched C1-C4 chain, optionally having one or more hydroxyl groups or C1-C4-alkoxy or C1-C4-acylamino groups. 10 Alkyl divalent group, -CH2-CHOH-CH2-O-R4-O-CH2-CHOH-CH2-, Alternatively, it may have one or more hydroxyl or C1-C4-alkoxy groups and be a divalent group obtained by removing two hydrogen atoms from two different atoms of a hydrocarbon, said hydrocarbon having up to 20 carbon atoms and containing at least one divalent group selected from the group consisting of: cycloalkylene, substituted cycloalkylene, phenylene, substituted phenylene, heteroalkylene, and substituted heteroalkylene; and

[0239] Each of R4, R5, and R6 is independently a straight-chain or branched C1-C bond with zero or one hydroxyl group. 10 Alkylene divalent group.

[0240] 19. The polysiloxane ethylene crosslinking agent as described in embodiment 18, wherein in formula (1), υ1 is an integer from 3 to 350.

[0241] 20. The polysiloxane ethylene crosslinking agent as described in embodiment 18, wherein in formula (1), υ1 is an integer from 5 to 300.

[0242] 21. The polysiloxane ethylene crosslinking agent as described in embodiment 18, wherein in formula (1), υ1 is an integer from 10 to 250.

[0243] 22. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 22, wherein, in formula (1), ω1 is an integer from 5 to 700.

[0244] 23. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 22, wherein, in formula (1), ω1 is an integer from 10 to 600.

[0245] 24. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 22, wherein, in formula (1), ω1 is an integer from 15 to 500.

[0246] 25. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 24, wherein a1 is zero in formula (1).

[0247] 26. The polysiloxane ethylene crosslinking agent as described in embodiment 25, wherein X0 is O in formula (1).

[0248] 27. The polysiloxane ethylene crosslinking agent as described in embodiment 25, wherein, in formula (1), X0 is NR N1 .

[0249] 28. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 27, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.30 to about 0.95.

[0250] 29. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 27, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.40 to about 0.90.

[0251] 30. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 27, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.50 to about 0.90.

[0252] 31. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 27, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.60 to about 0.85.

[0253] 32. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 31, wherein, in formula (1), AR is phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracene, substituted anthracene, phenanthrene, or substituted phenanthrene.

[0254] 33. The polysiloxane ethylene crosslinking agent as described in any one of embodiments 18 to 31, wherein, in formula (1), AR is Monovalent groups, of which R7, R8, R9, and R 10 R 11 R 12 and R 13 They are independently of each other H, Cl, Br, F, CF3, CCl3, C1-C5 alkyl, C1-C5 alkoxy, C2-C5 acyloxy, OH, phenyl, phenoxy, benzyloxy, phenyl carbonyl, phenoxy carbonyl, phenyl carboxyl (phenyl carbonyloxy), or naphthyl.

[0255] 34. An insert made of a hydrophobic crosslinked polymer material comprising repeating units of a polysiloxane ethylene crosslinker as described in any one of embodiments 1 to 33.

[0256] 35. An embedded siloxane hydrogel contact lens comprising a siloxane hydrogel body material and an insert as described in embodiment 34, wherein the insert is wholly or partially embedded within the siloxane hydrogel body material.

[0257] 36. A siloxane hydrogel contact lens comprising a siloxane hydrogel body material, said siloxane hydrogel body material comprising repeating units of a polysiloxane ethylene crosslinking agent as described in any one of embodiments 1 to 33.

[0258] 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 examples be considered exemplary.

[0259] Example 1

[0260] Oxygen permeability measurement

[0261] 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 ).

[0262] Balanced water content

[0263] The following measures the equilibrium water content (EWC) of the contact lens.

[0264] The amount of water (expressed as a percentage by weight) present in the hydrated hydrogel in a fully equilibrated saline solution was determined at room temperature. 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 plus lenses was removed from the oven 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 plus 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.

[0265] elastic modulus

[0266] The storage modulus (Young's modulus) of the insert was determined using a TA RSA-G2 DMA (Dynamic Mechanical Analyzer). The insert was cut into 3.08 mm wide strips using a Precision Concept dry lens cutter. Five thickness values ​​were measured over a 6.5 mm gauge length. The strip was mounted on an instrument with a metal clamp. An oscillating temperature ramp test was applied to the insert at a linear ramp rate of 2 °C / min from 10 °C to 50 °C, and the material's response to temperature increases was monitored at a constant frequency of 1 Hz, a constant amplitude of 0.5% deformation, and a sampling rate of 10.0 pts / s. The storage modulus (E'), loss modulus (E”), and tanδ data were calculated using TRIOS software.

[0267] 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. Typically, a 5 N load cell was 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 where elongation approaches zero.

[0268] Refractive index

[0269] The refractive index (RI) of the insert was determined using a Reichert Abbe Mark III laboratory refractometer at 25°C. The insert was fully equilibrated in PBS saline solution prior to measurement.

[0270] The refractive index (RI) of the polysiloxane-ethylene crosslinking agent was determined at 20°C using a Rudolph Research Analytical refractometer (model J357). The RI of distilled water (1.33299 at 20.0°C) was used as a reference and was measured before and after the polysiloxane-ethylene crosslinking agent measurements.

[0271] Glass transition temperature

[0272] The glass transition temperature (Tg) of the insert is defined as the peak value of tanδ obtained from the dynamic temperature ramp test using the TA RSA-G2 DMA (Dynamic Mechanical Analyzer).

[0273] According to this application, the glass transition temperature (Tg) of the polysiloxane ethylene crosslinking agent is the midpoint temperature in the differential scanning calorimetry plot obtained by using differential scanning calorimetry (DSC). Figure 1 The DSC diagram obtained for the polysiloxane ethylene crosslinking agent of the present invention is shown, and is characterized by its starting temperature, midpoint temperature, inflection point temperature and endpoint temperature.

[0274] Layering

[0275] For possible delamination, the embedded siloxane hydrogel contact lens is examined using an Optomec instrument or optical coherence tomography (OCT).

[0276] Regardless of the assessment method, after autoclaving and before stratification studies, contact lenses should be staged at room temperature for at least 12 hours.

[0277] After the required grading time has elapsed, place the fully hydrated contact lens into the "V" grid assembly of an Optimec instrument (OPTIMEC, UK, model JCF). After the contact lens has settled under gravity, carefully examine the front view of the contact lens for any indication of circular patterns. Grading appears as circular patterns in the Optimec image.

[0278] OCT (Thorlabs Optical Coherence Tomography, model Telesto-II) can also be used to study stratification. OCT allows for non-invasive imaging of contact lenses to obtain high-resolution cross-sectional images. For this purpose, after meeting the minimum stratification requirements, the contact lens is removed from its blister and immersed in PBS solution for at least 30 minutes to reach equilibration. Then, a cuvette with a "V" block feature is filled approximately 3 / 4 full with fresh PBS solution, and the contact lens is transferred into the cuvette using a cotton swab. The lens is allowed to float freely to the "V" shape at the bottom of the cuvette, and the entire contact lens is scanned in 10-degree increments. In the OCT images, stratification appears as cavitation in the spacer surface between the insert and the carrier.

[0279] chemicals

[0280] The following abbreviations are used in the following examples: BzA represents benzyl acrylate; BzMA represents benzyl methacrylate; DVBz represents divinylbenzene; p-STTMS represents styryltrimethoxysilane; PETA represents pentaerythritol tetraacrylate; TrisMA represents 3-[tris(trimethylsiloxy)silyl]propyl methacrylate; D6 represents monobutyl-terminated monomethacryloyloxypropyl-terminated polydimethylsiloxane (MW 600 to 800 g / mol, from Galleser); DMA represents N,N - Dimethylacrylamide; MMA represents methyl methacrylate; TEGDMA represents triethylene glycol dimethacrylate; Vazo-67 represents 2,2'-azobis(2-methylbutyronitrile); Ominirad-1173 represents a photoinitiator made from 2-hydroxy-2-methyl-1-phenylpropanone; Nobloc is 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate from Aldrich; RB247 is Reactive Blue 247 (2-acrylic acid, 2... -Methyl-,1,1'-[(9,10-dihydro-9,10-dioxo-1,4-anthratridiyl)bis(imino-2,1-ethanediyl)] ester); TAA represents tert-amyl alcohol; PrOH represents 1-propanol; IPA represents isopropanol; PPG represents poly(propylene glycol); EGBE represents ethylene glycol butyl ether; PBS represents phosphate-buffered saline with a pH of 7.2 ± 0.2 at 25°C and containing approximately 0.044 wt.% NaH2PO4·H2O and approximately 0.388 wt.% Na2HPO4· 2H2O and about 0.79 wt.% NaCl, where wt.% represents weight percentage; “H4” macromonomer represents a dimethacryloxypropyl-terminated polysiloxane having the formula (A) shown below (Mn about 11.3K-12.3Kg / mol, OH content about 1.82-2.01meq / g); “HA” macromonomer represents a dimethacryloxypropyl-terminated polysiloxane having the formula (A) shown below (Mn about 6.8Kg / mol, OH content about 1.2meq / g).

[0281]

[0282] Example 2

[0283] The hydrogen-containing siloxane polysiloxane (a precursor for preparing the polysiloxane ethylene crosslinking agent of the present invention) is prepared according to the procedure shown in Scheme 1.

[0284]

[0285] Option 1

[0286] Synthesis of polysiloxanes (Mn-5KD) containing hydrogen siloxanes

[0287] Weigh 602.05 g of octamethylcyclotetrasiloxane (D4), 510.32 g of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), and 92.81 g of 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane and premix them in a flask. Then, load the mixture into a 2-L jacketed reactor equipped with a mechanical motor, thermocouple, and nitrogen flow adapter. Add 2.4 g of trifluoromethanesulfonic acid to the stirred reaction mixture via pipette. Stir the reaction at 25°C for approximately 16 hours. After the reaction is complete, dilute the solution with 1000 mL of toluene and then neutralize with a solid base, followed by stirring for one hour. Filter the final mixture using a 0.45 μm glass microfiber filter. At this point, add BHT and MEHQ inhibitors (250 ppm each). Concentrate the polymer solution on a rotary evaporator and then under low vacuum to remove residual solvent. The resulting precursor was not purified and was determined to have a number-average molecular weight of approximately 5,000 g / mol and an average x of approximately 31 (by means of purification). 1 H NMR), and an average γ of approximately 32 (via H NMR), and approximately 32 γ (via H N 1 H NMR).

[0288] Synthesis of Hydrogen-Containing Polysiloxanes (Mn-3KD)

[0289] Weigh 100.19 g of octamethylcyclotetrasiloxane (D4), 247.39 g of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), and 51.32 g of 1,3-bis(3-methacryloyloxypropyl)-tetramethyldisiloxane and premix them in a flask. Then, load the mixture into a 1-L jacketed reactor equipped with a mechanical motor, thermocouple, and nitrogen flow adapter. Add 0.8 g of trifluoromethanesulfonic acid to the stirred reaction mixture via pipette. Stir the reaction at 25°C for approximately 16 hours. After the reaction is complete, dilute the solution with 200 mL of toluene and then neutralize it with a solid base, followed by stirring for one hour. Filter the final mixture using a 0.45 μm glass microfiber filter. At this point, add BHT and MEHQ inhibitors (250 ppm each). Concentrate the polymer solution on a rotary evaporator and then under low vacuum to remove residual solvent. The resulting precursor was not purified and was determined to have a number-average molecular weight of approximately 3,000 g / mol and an average x of approximately 9.4 (by means of...). 1 H NMR), and an average γ of approximately 28.1 (via H NMR). 1 HNMR).

[0290] Example 3

[0291] Synthesis of high-refractive-index polysiloxane ethylene crosslinking agents:

[0292]

[0293] A 500 mL jacketed reactor equipped with a mechanical stirrer, thermocouple, nitrogen feed, septum, and condenser was heated to 80 °C and purged with nitrogen at a rate of 100 mL / min for 30 min. Allyl phenyl ether (approximately 158.62 g, i.e., a 2:1 molar ratio relative to the hydrosiloxane unit), toluene (40 mL), and approximately 88.1 μL (approximately 25 ppm relative to the precursor) of Karstedt's catalyst solution were added to the reactor. The nitrogen flow rate was reduced to 50 mL / min. The hydrosiloxane-containing polysiloxane (Mn-3KD) (approximately 60.00 g) prepared in Example 2, the MEHQ inhibitor (0.0085 g), and toluene (60-80 mL) were added to a beaker and stirred for 10 min until the MEHQ dissolved. The solution was then transferred into two 100 mL Hamiltongas Tight syringes equipped with plastic sheaths. Each syringe containing approximately 70 mL of polymer solution was attached to a Harvard PHD infusion pump, and the feed line was inserted into the reactor via a rubber septum. A solution of the hydrosiloxane-containing polysiloxane in toluene was added via the syringe pump over 5 hours (at a rate of 0.2333 mL / min). The reactor temperature was maintained at 80 °C ± 2 °C throughout the reaction. After polymer addition, the reaction mixture was stirred for an additional 1 hour. Subsequently, IR scanning of the crude reaction mixture confirmed complete Si-H bond consumption. The reaction mixture was then cooled to room temperature, and the crude polymer was purified by thin-film distillation (hot finger temperature was 100 °C, achieved by reflux of water, with reduced pressure maintained at 1.3–1.9 mbar throughout the process). The collected polymer fraction had a T0 of -48 °C. g And a refractive index of 1.51553 (at 20°C). The final product's... 1 1H NMR spectroscopy showed that allyl phenyl ether was not present.

[0294] The hydrogen-containing siloxane polysiloxane (Mn-5KD) prepared in Example 2 was also used to prepare polysiloxane ethylene crosslinking agents according to the procedure described above. The resulting polysiloxane ethylene crosslinking agent has a refractive index of 1.49617 (at 20°C).

[0295] Example 4

[0296] This embodiment illustrates the synthesis of two high-refractive-index polysiloxane ethylene crosslinking agents (macromonomers).

[0297] A 500 mL jacketed reactor equipped with a mechanical stirrer, thermocouple, nitrogen feed, septum, and condenser was charged with phenothiazine (0.096 g), allyl benzyl ether (approximately 117.9 g) (at a molar ratio of approximately 1.6:1 to the hydrosiloxane unit), and toluene (59 mL). The reaction mixture was purged with nitrogen at room temperature at a rate of 100 mL / min for 30–40 min. Then, approximately 111.2 μL (approximately 40 ppm relative to the precursor) of a cassiterite catalyst solution was added to the reactor, and the reactor was heated to 95 °C while reducing the nitrogen flow rate to 50 mL / min.

[0298] The hydrosiloxane-containing polysiloxane (Mn-3KD; x≈9; y≈28) (approximately 48.0 g) prepared in Example 2 and toluene (24 mL) were added to a beaker, stirred for 10 min, and then transferred to a 100 mL Hamilton gas-tight syringe equipped with a plastic sheath. The syringe containing approximately 72 mL of polymer solution was attached to a Harvard PHD infusion pump, and the feed line was inserted into the reactor via a rubber septum. The hydrosiloxane-containing polysiloxane solution in toluene was added via the infusion pump over 2 hours (at a rate of 0.6 mL / min). The reactor temperature was maintained at 95 °C ± 2 °C throughout the reaction. After the polymer addition, the reaction mixture was stirred for an additional 1 h. Subsequently, IR scanning of the crude reaction mixture confirmed complete consumption of Si-H bonds. The reaction mixture was then cooled to room temperature, and the crude polymer was purified by extraction in a cyclohexane / acetonitrile system. The polymer dissolved in cyclohexane (bottom layer), and excess allyl benzyl ether partitioned to the acetonitrile layer. Typically, five extractions are performed to completely remove allyl benzyl ether. After extraction, 83.7 g of a clear, viscous, almost odorless amber fluid is collected.

[0299] During the optimization of the hydrosilylation reaction, a significant loss of terminal methacrylate double bonds, reaching up to 40%, was observed when allyl phenyl ether was used. Changing reaction conditions, such as temperature, stoichiometry, order of addition, and time of addition, did not improve the results. Even increasing the level of the inhibitor (phenothiazine) to up to 6000 ppm did not reduce the double bond loss, indicating that the methacrylate groups compete with the allyl component for C-Si bonds in the hydrosilylation reaction with silanes (Si-H). As a result of this competition, a significant increase in the viscosity of the final macromonomer was observed (Table 1). In extreme cases, the final polymer may be too viscous to be blended into formulations. However, very different results were observed when allyl phenyl ether was replaced with allyl benzyl ether. A very negligible loss of methacrylate double bonds was observed by NMR. The viscosity of the final macromonomer also became lower and easier to control. The results are reported in Table 1.

[0300] Table 1

[0301]

[0302] Example 5

[0303] Insertion materials

[0304] The polymerizable composition (insertion formulation) used for preparing the insert is prepared in air at room temperature by blending all components (materials) in the required amounts (parts by weight) to have the composition shown in Table 2.

[0305] Table 2

[0306]

[0307] Molded inserts

[0308] The insert formulation (polymerizable composition) was purged with nitrogen at room temperature for 30-35 minutes. The N2-purged polymerizable composition (30-40 mg) was then introduced into a polypropylene mold, which was closed and placed in an oven. The oven was configured as follows: a nitrogen supply unit was connected to the oven via a high-flow-capacity controller to control the flow rate of nitrogen through the oven; a vacuum pump was connected to the oven's exhaust line to control the differential pressure within the oven.

[0309] The insert formulation (polymerizable composition) in the mold is thermosetting in an oven under the following conditions: held for about 30 minutes at 25°C and an N2 flow rate of 80 scfh; gradually decreasing from 25°C to 55°C at a ramp rate of about 7°C / min; held for about 30 minutes at 55°C and an N2 flow rate of 40 scfh; gradually decreasing from 55°C to 80°C at a ramp rate of about 7°C / min; held for about 30 minutes at 80°C and an N2 flow rate of 40 scfh; gradually decreasing from 80°C to 100°C at a ramp rate of about 7°C / min; and held for about 30 minutes at 100°C and an N2 flow rate of 40 scfh. The mold is then opened and the molded insert is removed from the mold.

[0310] These inserts may or may not be extracted. Extract the inserts using the following procedure (if necessary). First, extract the inserts with PrOH for approximately 3 hours, rinse twice with deionized water for approximately 10 minutes each time, and dry in a vacuum oven at 50°C and 26 mm Hg for 1 hour. The insert obtained from insert formulation number 1 has an RI of approximately 1.50; the insert obtained from insert formulation number 2 has an RI of approximately 1.51; and the insert obtained from insert formulation number 3 has an RI of approximately 1.55.

[0311] SiHy lens fittings

[0312] The two SiHy lens formulations were prepared at room temperature in air by blending all components (materials) in the required amounts (parts by weight) to have the compositions shown in Table 3.

[0313] Table 3

[0314]

[0315] Preparation of SiHy contact lenses

[0316] The SiHy contact lens, which is produced by thermal or photochemical molding, is prepared as follows.

[0317] Molded components: A certain amount (approximately 50-60 mg) of the SiHy lens preparation prepared above is metered into the polypropylene female half mold, and then the polypropylene male half mold is placed on top of the female half mold, and the mold is firmly closed to form the molded assembly.

[0318] thermosetting The molded assembly (i.e., the closed mold in which the SiHy lens assembly is disposed) was thermocured in an oven under the following conditions: held at 25°C and an N2 flow rate of 80 scfh for about 30 minutes; gradually decreased from 25°C to 55°C at a ramp rate of about 7°C / min; held at 55°C and an N2 flow rate of 40 scfh for about 30 minutes; gradually decreased from 55°C to 80°C at a ramp rate of about 7°C / min; held at 80°C and an N2 flow rate of 40 scfh for about 30 minutes; gradually decreased from 80°C to 100°C at a ramp rate of about 7°C / min; and held at 100°C and an N2 flow rate of 40 scfh for about 30 minutes.

[0319] Photocuring Using approximately 1mW / cm 2 A high-intensity double-sided UV curing oven (Wicked Engineering, UV LED module 9W 365nm / 405nm) completely cured the molded assembly (i.e., the closed mold with SiHy lens assembly part number 5) for 10 minutes.

[0320] Demolding and lens removal The process involves mechanically opening the lens molds containing the molded, untreated SiHy contact lenses. The molded, untreated SiHy contact lenses are adhered to either the male or female mold. The untreated SiHy contact lenses adhered to the male mold are detached using an ultrasonic unit; the untreated SiHy contact lenses adhered to the female mold are manually detached.

[0321] Post-lens removal treatmentUntreated SiHy contact lenses, after lens removal, can be extracted with a 50:50 mixture of propylene glycol and water. Preferably, the untreated SiHy contact lenses are subjected to the following extraction / hydration, coating, and autoclaving treatment. The untreated SiHy contact lenses are immersed in a bath containing deionized water or a Tween 80 aqueous solution (500 PPM) for about 60 minutes, then immersed at 40°C in a bath containing an aqueous solution of polyacrylic acid (PAA, Mw450K) at a concentration of about 0.1% by weight for about 120 minutes; then immersed at room temperature in a bath containing a PBS solution for about 60 minutes; packaged / sealed in a 0.65 mL inner coating of packaging saline prepared according to the procedure described in Example 19 of US 8480227 in a polypropylene lens packaging shell (or blister pack) (one lens per shell); and finally autoclaved at 121°C for about 45 minutes. The resulting SiHy contact lenses each have a hydrogel coating thereon.

[0322] The lens properties of the resulting SiHy contact lens were determined according to the procedure described in Example 1 and are reported in Table 4.

[0323] Table 4

[0324]

[0325] Fabrication of fully embedded SiHy contact lenses

[0326] Embedded SiHy contact lenses, fabricated by thermal or photochemical casting, are prepared as follows.

[0327] Molded components: The insert prepared above is placed in the central region of the molding surface of the female mold (made of polypropylene), which preferably has three or more pins distributed in a circle with a diameter sufficient to accommodate the insert to fix the position of the insert on the molding surface. A certain amount (about 50-60 mg) of the SiHy lens preparation prepared above is metered into the female mold to immerse the insert. Then, the polypropylene male mold is placed on top of the female mold, and the mold is firmly closed to form the molding assembly.

[0328] thermosetting The molding components (i.e., closed molds, each having an insert therein immersed in the SiHy lens assembly) are thermosetting according to the procedure described above for preparing SiHy contact lenses.

[0329] Photocuring The molding components (i.e., closed molds, each having an insert in which the SiHy lens assembly number 5 is immersed) are completely photocured according to the procedure described for the preparation of SiHy contact lenses.

[0330] Demolding and lens removal As described above for the preparation of SiHy contact lenses, demolding and lens removal are performed.

[0331] Post-lens removal treatment The untreated embedded SiHy contact lenses are subjected to the extraction / hydration, coating, and autoclaving processes described above for the preparation of SiHy contact lenses. The resulting embedded SiHy contact lenses each have a hydrogel coating.

[0332] The obtained embedded SiHy contact lenses were examined for possible delamination using microscopy (i.e., OCT according to the procedure described in Example 1). No delamination was observed. The embedded SiHy contact lenses exhibited well-defined lens geometry without deformation after lens removal, extraction, coating, hydration, and autoclaving. It is believed that both the insert and the bulk SiHy material have a minimum swelling ratio upon hydration, resulting in minimal internal stress and therefore good geometric stability over time. The characterization of the embedded SiHy contact lenses is reported in Table 5.

[0333] Table 5

[0334]

[0335] 1. Directly determined using embedded SiHy contact lenses. 2. ΔRI = RI 插入物 -RI 本体

[0336] With a difference of at least about 0.07, the embedded SiHy contact lens of the present invention can be particularly used to prepare diffractive multifocal contact lenses.

[0337] Fabrication of partially embedded SiHy contact lenses

[0338] Embedded SiHy contact lenses, fabricated by thermal or photochemical casting, are prepared as follows.

[0339] The insert forming composition (insert formulation number 2) prepared above was purged with nitrogen at room temperature for 30 to 35 minutes. A specific volume (e.g., 30-40 mg) of the N2-purged insert forming composition was placed at the center of the molding surface of a negative lens half-mold made of polypropylene, the molding surface defining the front surface of the contact lens to be molded. The negative lens half-mold with the insert forming composition was closed with a positive insert half-mold made of polypropylene and designed with an overflow groove to form a first molding assembly, during which any excess insert forming composition was pressed into the overflow groove. The positive insert half-mold has a molding surface defining the rear surface of the insert to be molded. The oven was configured as follows: a nitrogen supply was connected to the oven via a high flow capacity controller that controlled the flow rate of nitrogen through the oven; a vacuum pump was connected to the oven's exhaust line to control the differential pressure within the oven.

[0340] The insert forming composition in the first molding assembly is thermosetting in an oven under the following conditions: gradually decreasing from room temperature to 55°C at a ramp rate of about 7°C / min; holding at 55°C for about 30-40 minutes; gradually decreasing from 55°C to 80°C at a ramp rate of about 7°C / min; holding at 55°C for about 30-40 minutes; gradually decreasing from 80°C to 100°C at a ramp rate of about 7°C / min; and holding at 100°C for about 30-40 minutes. The first molding assembly is then opened, and the molded insert is adhered to the central area of ​​the molded surface of the negative lens half-molding.

[0341] The lens forming composition (SiHy lens preparation number 1) prepared above was purged with nitrogen at room temperature for 30 to 35 minutes. A specific volume (e.g., 50-60 mg) of the N2-purged lens forming composition was placed on a molded insert adhered to the central portion of the molded surface of the negative lens half-mold. The negative lens half-mold, having the insert adhered thereto and the lens forming composition, was closed with a positive lens half-mold made of polypropylene and designed with an overflow groove to form a second molding assembly, during which any excess lens forming composition was pressed into the overflow groove. The positive lens half-mold has a molded surface defining the rear surface of the contact lens to be molded. The oven was configured as follows: a nitrogen supply unit was connected to the oven via a higher flow capacity controller, which controlled the flow rate of nitrogen through the oven; a vacuum pump was connected to the oven's exhaust line to control the differential pressure within the oven.

[0342] The closed second molding assembly, each having a molded insert in the lens forming composition immersed in the lens molding cavity, is thermo-cured in an oven under the following conditions: gradually decreasing from room temperature to 55°C at a ramp rate of about 7°C / min; holding at 55°C for about 30-40 minutes; gradually decreasing from 55°C to 80°C at a ramp rate of about 7°C / min; holding at 55°C for about 30-40 minutes; gradually decreasing from 80°C to 100°C at a ramp rate of about 7°C / min; and holding at 100°C for about 30-40 minutes. The second molding assembly, each having a molded, untreated embedded silicone hydrogel contact lens therein, is mechanically opened. The molded, untreated embedded silicone hydrogel contact lens is adhered to the male or female half-mold. An ultrasonic unit is used to remove the molded, untreated embedded silicone hydrogel contact lens adhered to the male mold; the molded, untreated embedded silicone hydrogel contact lens adhered to the female mold is removed manually from the female mold to which the lens is adhered.

[0343] The untreated embedded SiHy contact lenses, after lens removal, are subjected to the extraction / hydration, coating, and autoclaving processes described above for the preparation of SiHy contact lenses. The resulting embedded SiHy contact lenses each have a hydrogel coating on them.

[0344] Following the procedure described in Example 1, OCT was used to examine the resulting partially embedded SiHy contact lenses for possible delamination. No delamination was observed. The embedded SiHy contact lenses exhibited well-defined lens geometry without deformation after lens removal, extraction, coating, hydration, and autoclaving. It is believed that both the insert and the bulk SiHy material have a minimum swelling ratio upon hydration, resulting in minimal internal stress and therefore good geometric stability over time. The characterization of the embedded SiHy contact lenses is reported in Table 6.

[0345] Table 6

[0346]

[0347] 1. Directly determined using embedded SiHy contact lenses. 2. ΔRI = RI 插入物 -RI 本体

[0348] By having a difference of at least about 0.08, the partially embedded SiHy contact lens of the present invention can be specifically used to prepare diffractive multifocal contact lenses.

[0349] All publications, patents and patent applications cited above are incorporated herein by reference in their entirety.

Claims

1. A polysiloxane-ethylene crosslinking agent, comprising: (1) A polysiloxane segment comprising a dimethylsiloxane unit and an aryl-containing siloxane unit, the aryl-containing siloxane unit having a methyl substituent and an organic substituent having up to 45 carbon atoms and at least one aryl moiety, the aryl moiety being connected to a Si atom via a linker having at least 2 carbon atoms; and (2) Alkenyl unsaturated groups; The polysiloxane-ethylene crosslinking agent described herein has a refractive index of at least 1.48 and a Tc of 0°C or lower. g ; The polysiloxane segment comprises at least 30 mol% of the aryl-containing siloxane unit; The polysiloxane-ethylene crosslinking agent wherein the crosslinking agent has a number average molecular weight of at least 1000 Daltons; and The polysiloxane ethylene crosslinking agent mentioned above is defined by formula (1): in: υ1 is an integer between 1 and 400; ω1 is an integer from 1 to 800; E1 is Monovalent groups; R0 is either hydrogen or methyl; a1 is zero or 1; X0 is either O or NR N1 ; R N1 It is hydrogen or C1-C6 alkyl; L0 is a C2-C8 alkylene divalent group, or , , ,or divalent groups; L0' is a C2-C8 alkylene divalent group; "L0" is a C3-C8 alkylene divalent group; X1 is -O-, -NR N1 -、-NHCOO-、-OCONH-、-CONR N1 -or-NR N1 CO-; q1 is an integer from 1 to 10; AR stands for aryl; L AR yes divalent groups; L e yes , , , , , , , , , , , ,or divalent groups; a2 is zero, 1, or 2; a3 is zero or 1; R1 is a C1-C chain, whether straight or branched. 10 An alkylene divalent group, which may optionally be substituted with a C1-C4 alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an oxo group, or a combination thereof; R2 is a C1-C chain, whether straight or branched. 10 alkylene divalent groups; R3 is a C1-C4 alkylene divalent group that is either directly bonded, straight-chain, or branched; X AR Each X2 is independently covalently bonded, a straight-chain or branched C1-C4 alkylene divalent group, or covalently linked with the following: -O-, -S-, , , -NR N2 -, -NHCOO-, -OCONH-, -NHCONR N2 -、-NR N2 CONH-、 , , , , , -CONR N2 -、-NR N2 CO-、 , , , , , -NHCOS-, -SCONH-, -COO-, or -OCO-; R N2 It is hydrogen, straight-chain or branched C1-C6 alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted- or unsubstituted-phenyl-C1-C6 alkyl; Each L x Independently, it is a straight-chain or branched C1-C4 chain, optionally having one or more hydroxyl groups or C1-C4-alkoxy or C1-C4-acylamino groups. 10 alkylene divalent groups, , , Alternatively, it may have one or more hydroxyl or C1-C4-alkoxy groups and be a divalent group obtained by removing two hydrogen atoms from two different atoms of a hydrocarbon, said hydrocarbon having up to 20 carbon atoms and containing at least one divalent group selected from the group consisting of: cycloalkylene, substituted cycloalkylene, phenylene, substituted phenylene, heteroalkylene, and substituted heteroalkylene; and Each of R4, R5, and R6 is independently a straight-chain or branched C1-C bond with zero or one hydroxyl group. 10 Alkylene divalent group.

2. The polysiloxane ethylene crosslinking agent according to claim 1, wherein in formula (1), υ1 is an integer from 3 to 350.

3. The polysiloxane ethylene crosslinking agent according to claim 1, wherein in formula (1), ω1 is an integer from 5 to 700.

4. The polysiloxane ethylene crosslinking agent according to claim 2, wherein in formula (1), ω1 is an integer from 5 to 700.

5. The polysiloxane ethylene crosslinking agent according to claim 4, wherein a1 is zero in formula (1).

6. The polysiloxane ethylene crosslinking agent according to claim 1, wherein a1 is zero in formula (1).

7. The polysiloxane ethylene crosslinking agent according to claim 2, wherein a1 is zero in formula (1).

8. The polysiloxane ethylene crosslinking agent according to claim 3, wherein a1 is zero in formula (1).

9. The polysiloxane ethylene crosslinking agent according to claim 8, wherein in formula (1), X0 is O.

10. The polysiloxane ethylene crosslinking agent according to claim 8, wherein in formula (1), X0 is NR. N1 .

11. The polysiloxane ethylene crosslinking agent according to any one of claims 1 to 10, wherein in formula (1), ω1 / (υ1+ω1) is 0.30-0.

95.

12. The polysiloxane ethylene crosslinking agent according to any one of claims 1 to 10, wherein in formula (1), AR is phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracene, substituted anthracene, phenanthrene, or substituted phenanthrene.

13. The polysiloxane ethylene crosslinking agent according to any one of claims 1 to 10, wherein in formula (1), AR is or Monovalent groups, of which R7, R8, R9, and R 10 R 11 R 12 and R 13 They are independently of each other H, Cl, Br, F, CF3, CCl3, C1-C5 alkyl, C1-C5 alkoxy, C2-C5 acyloxy, OH, phenyl, phenoxy, benzyloxy, phenyl carbonyl, phenoxy carbonyl, phenyl carboxyl, or naphthyl.

14. An insert made of a crosslinked polymer material comprising repeating units of a polysiloxane ethylene crosslinking agent according to any one of claims 1 to 13.

15. An embedded siloxane hydrogel contact lens comprising a siloxane hydrogel body material and an insert according to claim 14, wherein the insert is wholly or partially embedded within the siloxane hydrogel body material.

16. A siloxane hydrogel contact lens comprising a siloxane hydrogel bulk material, said siloxane hydrogel bulk material comprising repeating units of a polysiloxane ethylene crosslinking agent according to any one of claims 1 to 13.

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