Ophthalmic and otorhinolaryngological device materials containing phenylene-siloxane macromers

1. A polymeric ophthalmic or otorhinolaryngological device material comprising

a) a monofunctional acrylate or methacrylate monomer of formula [1];

b) a difunctional acrylate or methacrylate cross-linking monomer of formula [2], and

c) a phenylene-siloxane macromer of formula [3a] or [3b]:

wherein:

B═O(CH 2 ) n , NH(CH 2 ) n , or NCH 3 (CH 2 ) n ;

R 1 , R 2 , R 3 independently ═H, CH 3 , CH 2 CH 3 , or CH 2 OH;

X, X′ independently ═O(CH 2 ) n , NH(CH 2 ) n , NCH 3 (CH 2 ) n , O(CH 2 ) n C 6 H 4 , O(CH 2 CH 2 O) n CH 2 , O(CH 2 CH 2 CH 2 O) n CH 2 , O(CH 2 CH 2 CH 2 CH 2 O) n CH 2 , or nothing;

J=(CH 2 ) a , O(CH 2 CH 2 O) b , O, or nothing, provided that if X and X′=nothing, then J≠nothing;

J′, J″ independently ═(CH 2 ) a or nothing, provided that if X and X′=nothing, then J′, J″≠nothing;

n=0-12;

Y═C 6 H 5 , (CH 2 ) m H, or O(CH 2 ) m C 6 H 5 ;

Z, Z′ independently ═C(=O) or OCH 2 C 6 H 4 ;

m=0-12;

a=1-12;

b=1-24;

R 4 , R 5 , R 6 , R 7 , R 8 , R 9 independently =(CH 2 ) b H, CH═CH 2 , CH═C(CH 3 ), CH 2 CH═CH 2 , CH 2 CH═CHCH 3 , CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , O(CH 2 ) m C 6 H 5 , O(CH 2 ) m C 6 H 4 (OH)C(O)C 6 H 5 , CH 2 CH 2 CH 2 NH 2 , CH 2 CH 2 CH 2 NHCH 3 , CH 2 CH 2 CH 2 N(CH 3 ) 2 , CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2 , CH 2 CH(CH 3 )CH 2 NHCH 2 CH 2 NH 2 , (CH 2 ) a OC(O)C(R 1 )═CH 2 , (CH 2 ) b SH, CH 2 CH 2 CH 2 OCH 2 (O)CH 2 , CH(CH 3 )NHCH 2 CH 3 , CH(CH 3 )N(CH 3 )CH 2 CH 3 , CH(CH 3 )N(CH 2 CH 3 ) 2 , cyclopentyl, cyclohexyl, CH 2 CH 2 CN, CH 2 CH 2 CH 2 CN, CH 2 CH 2 CH(CH 3 )CN, CH 2 Cl, CH 2 CH 2 Cl, CH 2 CH 2 CH 2 Cl, CH 2 CH 2 C 6 H 4 CH 2 Cl, CH 2 Si(CH 3 ) 3 , CH 2 Si(CH 2 CH 3 ) 3 , CH 2 CH 2 CF 3 , CH 2 NCO, CH 2 NHC 6 H 5 , C 6 F 5 , phenyl, or naphthyl, each optionally substituted with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 cycloalkyl, C 1 -C 12 cycloalkoxy, NO 2 , OH, CN, NCO, NH 2 , F, Br, Cl, I, or (CH 2 CH 2 O) b H;

R 10 =phenyl, biphenyl, diphenylether, or naphthyl, each optionally substituted with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 cycloalkyl, C 1 -C 12 cycloalkoxy, NO 2 , OH, CN, NCO, NH 2 , F, Br, Cl, I, or (CH 2 CH 2 O) b H; and

w=3-120.

2. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 wherein in formula [1]

B═O(CH 2 ) n ;

R 1 ═H or CH 3 ;

n=1-4; and

Y═C 6 H 5 .

3. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 wherein in formula [2]

R 2 , R 3 independently =H or CH 3 ;

X, X′ independently =O(CH 2 ) n , O(CH 2 ) n C 6 H 4 , or nothing;

J=O(CH 2 CH 2 O) b or nothing, provided that if X and X′=nothing,

then J≠nothing;

n=0-6; and

b=1-24.

4. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 wherein in formulas [3a] and [3b]

R 2 , R 3 independently =H or CH 3 ;

R 4 , R 5 , R 6 , R 7 independently =CH 3 or CH 2 CH 3 ;

R 8 , R 9 independently =CH 3 , phenyl, or naphthyl;

R 10 =phenyl, biphenyl, or naphthyl;

X, X′═O(CH 2 ) n , O(CH 2 CH 2 O) n CH 2 , O(CH 2 CH 2 CH 2 O) n CH 2 , O(CH 2 CH 2 CH 2 CH 2 O) n CH 2 , or nothing;

J′, J″=(CH 2 ) a ;

a=3-12;

Z, Z′═C(═O); and

w=3-90.

5. The polymeric ophthalmic or otorhinolaryngological device material of claim 4 wherein the phenylene-siloxane macromer is a macromer of formula [4a] or [4b]

wherein

R 2 , R 3 independently =H or CH 3 ;

R 8 , R 9 independently =CH 3 or phenyl;

J′, J″=(CH 2 ) a ;

a=3;

X, X′═O(CH 2 ) n ;

n=0;

Z, Z′═C(═O); and

w=10-70.

6. The polymeric ophthalmic or otorhinolaryngological device material of claim 3 wherein the monomer of formula [2] is selected from the group consisting of: ethylene glycol dimethacrylate (“EGDMA”); diethylene glycol dimethacrylate; 1,6-hexanediol dimethacrylate; 1,4-butanediol dimethacrylate; poly(ethylene oxide)dimethacrylate (number average molecular weight 200-1000); and their corresponding acrylates.

7. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 comprising 45 to 85% (w/w) of a monomer of formula [1].

8. The polymeric ophthalmic or otorhinolaryngological device material of claim 7 comprising 45 to 75% (w/w) of a monomer of formula [1].

9. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 comprising 1 to 95% (w/w) % of a macromer of formula [3a] or [3b].

10. The polymeric ophthalmic or otorhinolaryngological device material of claim 9 comprising 5 to 70% (w/w) of a macromer of formula [3a] or [3b].

11. The polymeric ophthalmic or otorhinolaryngological device material of claim 9 comprising 10 to 50% (w/w) of a macromer of formula [3a] or [3b].

12. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 comprising one or more ingredients selected from the group consisting of a polymerizable UV absorber and a polymerizable blue-light absorber.

13. The polymeric ophthalmic or otorhinolaryngological device material of claim 12 comprising 0.1 to 5% (w/w) of a polymerizable UV absorber.

14. The polymeric ophthalmic or otorhinolaryngological device material of claim 13 comprising 0.01-0.5% (w/w) of a polymerizable blue-light absorber.

15. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 wherein the device material has a refractive index in the dry state of at least 1.47.

16. An ophthalmic or otorhinolaryngological device comprising the device material of claim 1 wherein the ophthalmic or otorhinolaryngological device is selected from the group consisting of intraocular lenses; contact lenses; keratoprostheses; corneal inlays or rings; otological ventilation tubes; and nasal implants.

17. An intraocular lens comprising the device material of claim 1 .