Ophthalmic and otorhinolaryngological device materials

1. A polymeric ophthalmic or otorhinolaryngological device material comprising

a) 65 to 95% (w/w) of a monofunctional monomer of formula [1]:

wherein

B=—O(CH 2 ) n —, —(OCH 2 CH 2 ) n —; —NH(CH 2 ) n —, or —NCH 3 (CH 2 ) n —;

R 1 =H, CH 3 , CH 2 CH 3 , or CH 2 OH;

n=0-12;

A=C 6 H 5 or O(CH 2 ) m C 6 H 5 , where the C 6 H 5 group is optionally substituted with —(CH 2 ) n H, —O(CH 2 ) n H, —CH(CH 3 ) 2 , —C 6 H 5 , —OC 6 H 5 , —CH 2 C 6 H 5 , F, Cl, Br, or I; and

m=0-18;

b) a difunctional cross-linking monomer of formula [2]:

wherein

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

W, W′ independently=O(CH 2 ) d , NH(CH 2 ) d , NCH 3 (CH 2 ) d , O(CH 2 ) d C 6 H 4 , O(CH 2 CH 2 O) d CH 2 , O(CH 2 CH 2 CH 2 O) d CH 2 , O(CH 2 CH 2 CH 2 CH 2 O) d CH 2 , or nothing;

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

d=0-12;

a=1-12; and

b=1-24;

and

c) 5 to 35% (w/w) of a hydrophilic side-chain macromer of formula [3a], [3b], [3c], [3d], or [3e]:

wherein for formulas [3a], [3b], [3c], [3d], and [3e]

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

e, f independently=1-100;

X, X 1 , X 2 independently=O, NH—, N(CH 3 )—, N(CH 2 CH 3 )—, or N(C 6 H 5 )—;

Y, Y 1 independently=—H, —(CH 2 ) p H, —CHC(CH 3 ) 2 , —CH 2 CH 2 N(CH 3 ) 2 , —CH 2 CH 2 N(CH 2 CH 3 ) 2 , CH 2 CH 2 N(C 6 H 5 ) 2 , —CH 2 CH(OH)CH 2 OH, CH 2 CH(OH)CH 2 OC 6 H 5 , (CH 2 CH 2 O) q CH 3 , (CH 2 CH 2 O) q H, (CH 2 CH 2 O) q C 6 H 5 , (CH 2 ) t C 6 H 5 , (CH 2 ) t OC 6 H 5 , or CH 2 CH 2 N(—C(O)CH 2 CH 2 CH 2 —),

provided that Y≠Y 1 ,

and further provided that at least one of Y and Y 1 ═CH 2 CH 2 N(CH 3 ) 2 , —CH 2 CH 2 N(CH 2 CH 3 ) 2 , CH 2 CH 2 N(C 6 H 5 ) 2 , —CH 2 CH(OH)CH 2 OH, CH 2 CH(OH)CH 2 OC 6 H 5 , (CH 2 CH 2 O) q CH 3 , (CH 2 CH 2 O) q H, (CH 2 CH 2 O) q C 6 H 5 , or CH 2 CH 2 N(—C(O)CH 2 CH 2 CH 2 —); and the other of Y and Y 1 =—H, —(CH 2 ) p H, —CHC(CH 3 ) 2 , (CH 2 CH 2 O) q C 6 H 5 , (CH 2 ) t C 6 H 5 , or (CH 2 ) t OC 6 H 5 ;

p=1-18;

q=1-230;

t=0-6;

R 4 ═CH 3 OC(O)CH(CH 3 )—, CH 3 OC(O)C(CH 3 ) 2 —, HOCH 2 CH 2 OC(O)C(CH 3 ) 2 —, (CH 2 ═C(R 3 )CO 2 CH 2 CH 2 OC(O)C(CH 3 ) 2 —, CH 3 CH 2 OC(O)CH(CH 3 )—, CH 3 CH 2 OC(O)C(CH 3 ) 2 —, CH 3 OC(O)CH(CH 2 CH 3 )—, CH 3 CH 2 OC(O)CH(CH 2 CH 3 )—, CH 2 ═CHCH 2 OC(O)C(CH 3 ) 2 —, CH 3 CH 2 OC(O)CH(CH 2 CH 2 CH 3 )—, CH 3 OC(O)CH(CH 2 CH 2 CH 2 CH 3 )—, [CH 3 OC(O)] 2 CH—, [CH 3 CH 2 OC(O)] 2 CH—, [CH 3 CH 2 OC(O)] 2 C(CH 3 )—, CH 3 CH 2 OC(O)CH(CH 2 CH 2 CH 2 CH 3 )—, (CH 3 ) 3 COC(O)C(CH 3 ) 2 —, CH 3 CH 2 OC(O)CH 2 CH 3 (CH 2 CH 2 CH 2 CH 3 )—, CH 3 CH 2 OC(O)CH(CH 2 CH 2 CH 2 CH 2 CH 3 )—, CH 3 CH 2 OC(O)CH(CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 )—,

provided that in the case of formula [3e], R 4 is selected from the group consisting of (CH 2 ═C(R 3 )CO 2 CH 2 CH 2 OC(O)C(CH 3 ) 2 —, and CH 2 ═CHCH 2 OC(O)C(CH 3 ) 2 —,

or

g, g′ independently=1-12; and

L=H, Cl, Br, —CH 2 C(O)CH 3 , CH 2 C(O)C(CH 3 ) 3 , —CH 2 C(O)C 6 H 5 , —CH 2 C(O)C 6 H 4 OH, —CH 2 C(O)C 6 H 4 OCH 3 ,

 or CH 2 CH═CH 2 .

2. The polymeric device material of claim 1 wherein for the monomer of formula [1]:

B=—O(CH 2 ) n — or —(OCH 2 CH 2 ) n —;

R 1 =—H or —CH 3 ;

n=1-5;

A=—C 6 H 5 , O(CH 2 ) m C 6 H 5 ; and

m=0-4.

3. The polymeric device material of claim 1 wherein for the monomer of formula [2]:

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

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

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

d=0-6; and

b=1-10.

4. The polymeric device material of claim 1 wherein for the macromer Of formula [3]:

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

e, f independently=5-75;

X, X 1 , X 2 independently=O or N(CH 3 )—;

Y, Y 1 independently=—(CH 2 ) p H, (CH 2 CH 2 O) q CH 3 , (CH 2 CH 2 O) q H, (CH 2 CH 2 O) q C 6 H 5 , (CH 2 ) t C 6 H 5 , or (CH 2 ) t OC 6 H 5 ;

p=1-12;

q=2-60;

t=1-5;

R 4 =CH 3 OC(O)CH(CH 3 )—, CH 3 OC(O)C(CH 3 ) 2 —, HOCH 2 CH 2 OC(O)C(CH 3 ) 2 —, (CH 2 ═C(R 3 )CO 2 CH 2 CH 2 OC(O)C(CH 3 ) 2 —, CH 3 CH 2 OC(O)CH(CH 3 )—, CH 3 CH 2 OC(O)C(CH 3 ) 2 —, CH 3 OC(O)CH(CH 2 CH 3 )—, CH 3 CH 2 OC(O)CH(CH 2 CH 3 )—, (CH 3 ) 3 COC(O)C(CH 3 ) 2 —,

provided that in the case of formula [3e], R 4 is (CH 2 ═C(R 3 )CO 2 CH 2 CH 2 OC(O)C(CH 3 ) 2 —;

g, g′ independently=1-12; and

L=H, Cl, Br, —CH 2 C(O)CH 3 , CH 2 C(O)C(CH 3 ) 3 , —CH 2 C(O)C 6 H 5 , —CH 2 C(O)C 6 H 4 OH, —CH 2 C(O)C 6 H 4 OCH 3 ,

 or CH 2 CH═CH 2 .

5. The polymeric device material of claim 4 wherein for the macromer of formula [3]:

e, f independently=5-60;

X, X 1 , X 2 =O;

Y, Y 1 independently=—(CH 2 CH 2 O) q CH 3 , (CH 2 CH 2 O) q C 6 H 5 , (CH 2 ) t C 6 H 5 , or (CH 2 ) t OC 6 H 5 ;

q=2-40;

t=1-2;

R 4 ═CH 3 OC(O)CH(CH 3 )—, CH 3 OC(O)C(CH 3 ) 2 —, HOCH 2 CH 2 OC(O)C(CH 3 ) 2 —,

(CH 2 ═C(R 3 )CO 2 CH 2 CH 2 OC(O)C(CH 3 ) 2 —, or CH 3 OC(O)CH(CH 2 CH 3 )—;

provided that in the case of formula [3e], R 4 is (CH 2 ═C(R 3 )CO 2 CH 2 CH 2 OC(O)C(CH 3 ) 2 —;

g, g′ independently=1-6; and

L=H, —CH 2 C(O)C 6 H 5 , —CH 2 C(O)C 6 H 4 OH, —CH 2 C(O)C 6 H 4 OCH 3 , or CH 2 CH═CH 2 .

6. The polymeric device material of claim 1 wherein the monomer of formula [1] is selected from the group consisting of benzyl methacrylate; 2-phenylethyl methacrylate; 3-phenylpropyl methacrylate; 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate; 2-phenoxyethyl methacrylate; 2-(2-henoxyethoxy)ethyl methacrylate; 2-benzyloxyethyl methacrylate; 2-(2-(benzyloxy)ethoxy)ethyl methacrylate; 3-benzyloxypropyl methacrylate; benzyl acrylate; 2-phenylethyl acrylate; 3-phenylpropyl acrylate; 4-phenylbutyl acrylate; 5-phenylpentyl acrylate; 2-phenoxyethyl acrylate; 2-(2-phenoxyethoxy)ethyl acrylate; 2-benzyloxyethyl acrylate; 2-(2-(benzyloxy)ethoxy)ethyl acrylate; and 3-benzyloxypropyl acrylate.

7. The polymeric device material of claim 1 wherein the monomer of formula [2] is selected from the group consisting of ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; triethylene glycol dimethacrylate; 1,6-hexanediol dimethacrylate; 1,4-butanediol dimethacrylate; 1,4-benzenedimethanol dimethacrylate; ethylene glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; 1,6-hexanediol diacrylate; 1,4-butanediol diacrylate; and 1,4-benzenedimethanol diacrylate.

8. The polymeric device material of claim 1 wherein the amount of monomer [1] is 70 to 90% (w/w).

9. The polymeric device material of claim 1 wherein the amount of monomer [2] is 0.5 to 3% (w/w).

10. The polymeric device material of claim 1 wherein the amount of hydrophilic side-chain macromer is 10 to 30% (w/w).

11. The polymeric device material of claim 10 wherein the amount of hydrophilic side-chain macromer is 10 to 20% (w/w).

12. The polymeric device material of claim 1 wherein the hydrophilic side-chain macromer is a macromer of formula [3a].

13. The polymeric device material of claim 1 wherein the hydrophilic side-chain macromer is a macromer of formula [3b].

14. The polymeric device material of claim 1 wherein the hydrophilic side-chain macromer is a macromer of formula [3c].

15. The polymeric device material of claim 1 wherein the hydrophilic side-chain macromer is a macromer of formula [3d].

16. The polymeric device material of claim 1 wherein the hydrophilic side-chain macromer is a macromer of formula [3e].

17. The polymeric device material of claim 1 further comprising an ingredient selected from the group consisting of a polymerizable UV absorber and a polymerizable colorant.

18. The polymeric device material of claim 17 comprising 0.1-5% (w/w) of a polymerizable UV absorber and 0.01-0.5% (w/w) of a polymerizable colorant.

19. An ophthalmic or otorhinolaryngological device comprising the polymeric 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.

20. The ophthalmic or otorhinolaryngological device of claim 19 wherein the ophthalmic or otorhinolaryngological device is an intraocular lens.