Water-processable silicone-containing prepolymers and uses thereof

A water-processable prepolymer, comprising:

• (1) siloxane-containing monomeric units and/or polysiloxane-containing crosslinking units, wherein the siloxane-containing monomeric units are derived from one or more siloxane-containing vinylic monomers each having at least one hydrophilic polymeric chain with a molecular weight of up to about 10000 Daltons, wherein the polysiloxane-containing crosslinking units are derived from at least one hydrophilized polysiloxane crosslinker and/or chain-extended hydrophilized polysiloxane crosslinker each having one or more pendant hydrophilic polymeric chains;
• (2) hydrophilic monomeric units derived from one or more hydrophilic vinylic monomers;
• (3) from about 0.05% to about 5% by weight of polymerizable units each having a pendant or terminal, ethylenically-unsaturated group and free of any polysiloxane segment;
• and
• (4) optionally hydrophobic units derived from at least one hydrophobic vinylic monomer free of silicone,
• wherein the prepolymer comprises the polysiloxane-containing crosslinking units derived from a hydrophilized polysiloxane or chain-extended polysiloxane crosslinker of formula (7) or (8)
• In which
• d2, d3, d4, ω1, ω2, and ω3 independent of one another are an integer from 0 to 20;
• e3, e4, e5, e6, e7, ν1, ν2, ν3, ν4, and ν5 independent of one other are 0, 1, 2 or 3 and (e3+e4+e5+e6+e7)≧1 and (ν1+ν2+ν3+ν4+ν5)≧1;
• X1 is hydrogen or methyl;
• D3, D4, D5, D6, D7, D8, D9 and D10 independently of one other are a divalent group of formula (9)
• in which Y28 is as defined below, A8, A8′, A9′, and A9′ independent of one other are a direct bond, a linear or branched C1-C10 alkylene divalent radical, —(CH2CH2O)r1—CH2CH2— in which r1 is an integer of 1 to 20, or a C1-C7 alkyleneoxy-C1-C7 alkylene divalent radical, and R1, R2, R3, R4, R5, R6, R7, R8, R1′, R2′, R3′, R4′, R5′, R6′, R7′, and R8′ independently of one another, are C1-C4-alkyl, -alk-(OCH2CH2)r2—OR9 in which alk is C1-C6-alkylene divalent radical, R9 is C1-C4 alkyl and r2 is an integer from 1 to 20, f1 is an integer of 0 to 8, m1, m2, p1 and p2 independently of each other are an integer of from 0 to 150, (m1+p1) and (m2+p2) independent of each other are from 2 to 150;
• L4, L5, L6, L7, L8, L9, L10, L11, L12, L13, L14, L15, L16, L17, Y8, Y9, Y10, Y11, Y12, Y13, Y14, Y15, Y16, Y17, Y18, Y19, Y20, Y21, Y22, Y23, Y24, Y25, Y26, Y27, and Y28 independent of one another are a direct bond or a divalent radical of
• —Z1—X2—Z2—X3—Z3—X4—Z4— In which X2, X3 and X4 independent of one other are a linkage selected from the group consisting of a direct bond —O—, —NR′— in which R′ is H or C1-C4 alkyl, —C(O)—NH—, —NH—C(O)—, —NH—C(O)—NH—, —O—C(O)—NH—, —S—, —NH—C(O)—O—, —C(O)—O—, —O—C(O)—, —NH—C(O)—NH—Z0—NH—C(O)—NH—, —O—C(O)—NH—Z0—NH—C(O)—O—, —O—C(O)—NH—Z0—NH—C(O)—NH—, and —NH—C(O)—NH—Z0—NH—C(O)—O—, Z0 is a linear or branched C2-C12 alkylene divalent radical or a C5-C45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—, Z1, Z2, Z3 and Z4 independent of one other are is a direct bond, a linear or branched C1-C12 alkylene divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—, a divalent radical of —CH2—CH(OH)—CH2— or —(CH2CH2O)r1—CH2CH2— with r1 as defined above, or a C5-C45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—;
• B5, B6, B7, B8, B9, B10, B11, B12, B13, and B14 independent of one another are hydroxyl or a linear or 3-arm hydrophilic polymer chain having a molecular weight of about 10000 Daltons or less and comprising at least about 60% by weight of one or more hydrophilic monomeric units selected from the group consisting of ethyleneoxide units, (meth)acrylamide units, C1-C3 alkyl (meth)acrylamide units, di-(C1-C3 alkyl) (meth)acrylamide units, N-vinylpyrrole units, N-vinyl-2-pyrrolidone units, 2-vinyloxazoline units, 4-vinylpyridine units, mono-C1-C4 alkoxy, mono-(meth)acryloyl terminated polyethyleneglycol units having a molecular weight of 600 Daltons or less, di(C1-C3 alkyl amino)(C2-C4 alkyl) (meth)acrylate units, N—C1-C4 alkyl-3-methylene-2-pyrrolidone units, N—C1-C4 alkyl-5-methylene-2-pyrrolidone units, N-vinyl C1-C6 alkylamide units, N-vinyl-N—C1-C6 alkyl amide units, and combinations thereof, provided that at least one of B5, B6, B7, B8, and B9 and at least one of B10, B11, B12, B13, and B14 are the linear or 3-arm hydrophilic polymer chain;
• and
• T1, T2, T3, T4, T5, T6, T7, T8, T9, T10, T11, T12, T13, and T14 independent of one another are an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic trivalent radical which has up to 15 carbon atoms and can be interrupted by —O—, —NR′—, —C(O)— and/or —S—,
• wherein the prepolymer comprises from about 20% to about 50% by weight of silicone relative to the total weight of the prepolymer and has a high water solubility or dispersibility of at least about 5% by weight in water, wherein the prepolymer is capable of being actinically crosslinked, in the absence of one or more vinylic monomers, to form a silicone hydrogel contact lens having a water content of from about 20% to about 75% by weight when fully hydrated, an oxygen permeability (Dk) of at least about 40 barrers, and optionally a hydrophilic surface characterized by an average water contact angle of about 90 degrees or less without post-molding surface treatment.