Actinically-crosslinkable amphiphilic prepolymers

1. A medical device, comprising a silicone hydrogel material that is obtained by actinically crosslinking a polymerizable material which comprises:

(a) an actinically crosslinkable prepolymer of formula (1)

in which

B 1 , B 2 , B 3 , B 4 , and B 5 independent of one another are a linear hydrophilic polymer chain of

 in which 1 R is hydrogen, methyl or ethyl group, A′ is C 1 -C 4 alkoxy and q is an integer from 3 to 200, and have a weight average molecular weight of about 10000 Daltons or less,

d1, d2, d3 independent of one another are an integer from 0 to 20 and (d1+d2+d3)≧1,

D 1 , D 2 , D 3 , and D 4 independently of one other are a divalent group of formula (2)

in which A 1 and A 2 independent of each other are a direct bond, a linear or branched C 1 -C 10 alkylene radical, —(CH 2 CH 2 O) r1 —CH 2 CH 2 — in which r1 is an integer of 1 to 20, or a C 1 -C 7 alkyleneoxy-C 1 -C 7 alkylene divalent radical, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , independently of one another, are C 1 -C 10 alkyl, C 1 -C 4 alkyl- or C 1 -C 4 -alkoxy-substituted phenyl, C 1 -C 10 fluoroalkyl, C 1 -C 10 fluoroether, C 6 -C 18 aryl radical, -alk-(OCH 2 CH 2 ) n —OR 9 in which alk is C 1 -C 6 -alkylene divalent radical, R 9 is hydrogen or C 1 -C 5 alkyl and n is an integer from 1 to 10, m and p independently of each other are an integer of from 0 to 100 and (m+p) is from 1 to 100,

e1, e2, e3, e4, e5 independent of one other are an integer from 0 to 3 and (e1+e2+e3+e4+e5)≧1,

L 1 , L 2 , L 3 , L 4 , and L 5 independent of one another are a direct bond or a divalent radical of —Z 1 —X 1 —Z 2 —X 2 —Z 3 —X 3 —Z 4 —

in which

 X 1 , X 2 , and X 3 independent of one other are a linkage selected from the group consisting of a direct bond, —O—, —NR′— in which R′ is H or C 1 -C 4 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—Z 0 —NH—C(O)—O—NH—, —O—C(O)—NH—Z 0 —NH—C(O)—O—, —O—C(O)—NH—Z 0 —NH—C(O)—NH—, and —NH—C(O)—NH—Z 0 —NH—C(O)—O—, Z 0 is a linear or branched C 2 -C 12 alkylene divalent radical or a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′— with R′ as defined above, —S— and —C(O)—, Z 1 , Z 2 , Z 3 , and Z 4 independent of one other are a direct bond, a linear or branched C 1 -C 12 alkylene divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—, —(CH 2 CH 2 O) r1 —CH 2 CH 2 — with r1 as defined above, or a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′— with R′ as defined above, —S— and —C(O)—,

Y 1 , Y 2 , Y 3 , Y 4 , Y 4 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 each comprise at least one urethane linkage (—O—C(O)—NH—) and independent of each other are a divalent radical of —Z 1 —X 1 —Z 2 —X 2 —Z 3 —X 3 —Z 4 — as defined above, or a divalent radical of formula (3)

in which

 Z 1 to Z 4 and X 1 to X 3 are as defined above,

 X 4 , X 5 , and X 6 independent of one other are a linkage selected from the group consisting of a direct bond, —O—, —NR′— with R′ as defined above, —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—Z 0 —NH—C(O)—NH— with Z 0 as defined above, —O—C(O)—NH—Z 0 —NH—C(O)—O— with Z 0 as defined above, —O—C(O)—NH—Z 0 —NH—C(O)—NH— with Z 0 as defined above, and —NH—C(O)—NH—Z 0 —NH—C(O)—O— with Z 0 as defined above,

 Z 5 , Z 6 , Z 7 , and Z 8 independent of one other are a direct bond, a linear or branched C 1 -C 12 alkylene divalent radical optionally containing therein one or more linkages of —O—, —NR′— with R′ as defined above, —S— and —C(O)—, —(CH 2 CH 2 O) r1 —CH 2 CH 2 — with r1 as defined above, or a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′— with R′ as defined above, —S— and —C(O)—,

  1 R is hydrogen, methyl or ethyl group, and

 q is an integer from 3 to 200,

T 1 , T 2 , T 3 , T 4 , and T 5 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′— with R′ as defined above, —C(O)— and/or —S—, and

Q is defined by any one of formula (I)-(III)

in which (i) R 10 -R 17 , independent of each other, are hydrogen, C 1 -C 10 alkene divalent radical, C 1 -C 10 alkyl, or —(R 18 ) a1 —(X 7 ) b1 —R 19 in which R 18 is C 1 -C 10 alkene divalent radical, X 7 is an ether linkage, a urethane linkage, a urea linkage, an ester linkage, an amid linkage, or carbonyl, R 19 is hydrogen, a single bond, amino group, carboxylic group, hydroxyl group, carbonyl group, C 1 -C 12 aminoalkyl group, C 1 -C 18 alkylaminoalkyl group, C 1 -C 18 carboxyalkyl group, C 1 -C 18 hydroxyalkyl group, C 1 -C 18 alkylalkoxy group, C 1 -C 12 aminoalkoxy group, C 1 -C 18 alkylaminoalkoxy group, C 1 -C 18 carboxyalkoxy group, or C 1 -C 18 hydroxyalkoxy group, a1 and b1 independent of each other is zero or 1, q1 is 1, provided that only one of R 10 -R 17 are divalent radicals; (ii) R 20 -R 25 , independent of each other, are hydrogen, C 1 -C 10 alkene divalent radical, C 1 -C 10 alkyl, or —(R 18 ) a1 —(X 7 ) b1 —R 19 in which R 18 , R 19 , X 7 , a1, and b1 are as defined above, provided that at least one of R 20 -R 25 are divalent radicals, t1 and t2 independent of each other are integer number from 0 to 9, provided that (t1+t2) is an integer number from 2 to 9; (iii) R 26 is hydrogen, or C 1 -C 10 alkyl; R 27 and R 28 independent of each other are hydrogen, C 1 -C 10 alkyl, or —(R 18 ) a1 —(X 7 ) b1 —R 19 in which R 18 , R 19 , X 7 , a1, and b1 are as defined above, R 29 is a C 1 -C 10 alkene divalent radical; and

(b) at least one crosslinking/branching agents having multiple thiol groups, based on step-growth polymerization mechanism.

2. The medical device of claim 1 , wherein the medical device is a soft contact lens which has at least one property selected from the group consisting of: an oxygen permeability of at least 40 barrers; an elastic modulus of from 0.1 MPa to about 2.0 MPa; a water content of from about 15% to about 70% by weight when fully hydrated; and combinations thereof.

3. A method for producing soft contact lenses, comprising the steps of:

(1) providing a mold for making a soft contact lens, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens and a second mold half with a second molding surface defining the posterior surface of the contact lens, wherein said first and second mold halves are configured to receive each other such that a cavity is formed between said first and second molding surfaces;

(2) introducing a lens-forming material into the cavity, wherein the lens-forming material comprises at least one actinically crosslinkable amphiphilic prepolymer of claim 1 and at least one crosslinking/branching agents having multiple thiol groups; and

(3) actinically irradiating the lens forming material in the cavity to form a contact lens.

4. The method of claim 3 , wherein the lens-forming material further comprises a prepolymer having multiple acryloyl

or methacryloyl

groups.

5. The method of claim 3 , wherein the lens-forming material comprise at least one component selected from the group consisting of a photoinitiator, a polymerizable UV-absorbing agent, a visibility tinting agent, antimicrobial agents, a bioactive agent, leachable lubricants, leachable tear-stabilizing agents, and mixtures thereof.

6. The method of claim 5 , wherein the mold is a reusable mold and the lens-forming material is cured actinically under a spatial limitation of actinic radiation to form a soft contact lens.

7. The method of claim 6 , wherein crosslinking of the lens-forming material in the mold is in a time period of about 60 seconds or less.

8. The medical device of claim 1 , wherein the prepolymer is represented by formula (5)

in which Q, D 1 , D 2 , L 1 , T 2 , 1 R, q, Y 1 , Y 3 , Y 4 , and Y 10 are as defined in claim 1 , e2 is an integer from 1 to 3, d1 is an integer from 1 to 20, and A′ is C 1 -C 4 alkoxy.

9. The medical device of claim 1 , wherein the prepolymer is represented by formula (6)

in which Q, D 1 to D 4 , X 1 to X 6 , e2, e4, d1, d3, Z 1 to Z 8 , 1 R, q, L 2 , L 4 , T 2 , T 4 , B 2 , B 4 , Y 1 , Y 3 , Y 4 , Y 7 , Y 8 , and Y 10 are as defined in claim 1 , and d2 is an integer from 1 to 20.

10. The medical device of claim 1 , wherein in formula (1) Q is defined by formula (I)

in which R 10 -R 17 , independent of each other, are hydrogen, C 1 -C 10 alkene divalent radical, C 1 -C 10 alkyl, or —(R 18 ) a —(X 1 ) b —R 19 in which R 18 is C 1 -C 10 alkene divalent radical, X 1 is an ether linkage, a urethane linkage, a urea linkage, an ester linkage, an amid linkage, or carbonyl, R 19 is hydrogen, a single bond, amino group, carboxylic group, hydroxyl group, carbonyl group, C 1 -C 12 aminoalkyl group, C 1 -C 18 alkylaminoalkyl group, C 1 -C 18 carboxyalkyl group, C 1 -C 18 hydroxyalkyl group, C 1 -C 18 alkylalkoxy group, C 1 -C 12 aminoalkoxy group, C 1 -C 18 alkylaminoalkoxy group, C 1 -C 18 carboxyalkoxy group, or C 1 -C 18 hydroxyalkoxy group, a and b independent of each other is zero or 1, p is 1, provided that only one of R 10 -R 17 are divalent radicals.

11. The medical device of claim 1 , wherein in formula (1) Q is being defined by formula (II)

in which R 20 -R 25 , independent of each other, are hydrogen, C 1 -C 10 alkene divalent radical, C 1 -C 10 alkyl, or —(R 18 ) a —(X 1 ) b —R 19 , optionally R 4 and R 9 are linked through an alkene divalent radical to form a cyclic ring, provided that at least one of R 20 -R 25 are divalent radicals, t1 and t2 independent of each other are integer number from 0 to 9, provided that (t1+t2) is an integer number from 2 to 9.

12. The medical device of claim 2 , wherein the prepolymer is represented by formula (5)

in which Q, D 1 , D 2 , L 1 , T 2 , 1 R, q, Y 1 , Y 3 , Y 4 , and Y 10 are as defined in claim 1 , e2 is an integer from 1 to 3, d1 is an integer from 1 to 20, and A′ is C 1 -C 4 alkoxy.

13. The medical device of claim 2 , wherein the prepolymer is represented by formula (6)

in which Q, D 1 to D 4 , X 1 to X 6 , e2, e4, d1, d3, Z 1 to Z 8 , 1 R, q, L 2 , L 4 , T 2 , T 4 , B 2 , B 4 , Y 1 , Y 3 , Y 4 , Y 7 , Y 8 , and Y 10 are as defined in claim 1 , and d2 is an integer from 1 to 20.

14. The medical device of claim 10 , wherein in formula (1) Q is defined by formula (I)

in which R 10 -R 17 , independent of each other, are hydrogen, C 1 -C 10 alkene divalent radical, C 1 -C 10 alkyl, or —(R 18 ) a —(X 1 ) b —R 19 in which R 18 is C 1 -C 10 alkene divalent radical, X 1 is an ether linkage, a urethane linkage, a urea linkage, an ester linkage, an amid linkage, or carbonyl, R 19 is hydrogen, a single bond, amino group, carboxylic group, hydroxyl group, carbonyl group, C 1 -C 12 aminoalkyl group, C 1 -C 18 alkylaminoalkyl group, C 1 -C 18 carboxyalkyl group, C 1 -C 18 hydroxyalkyl group, C 1 -C 18 alkylalkoxy group, C 1 -C 12 aminoalkoxy group, C 1 -C 18 alkylaminoalkoxy group, C 1 -C 18 carboxyalkoxy group, or C 1 -C 18 hydroxyalkoxy group, a and b independent of each other is zero or 1, p is 1, provided that only one of R 10 -R 17 are divalent radicals.

15. The medical device of claim 2 , wherein in formula (1) Q is being defined by formula (II)

in which R 20 -R 25 , independent of each other, are hydrogen, C 1 -C 10 alkene divalent radical, C 1 -C 10 alkyl, or —(R 18 ) a —(X 1 ) b —R 19 , optionally R 4 and R 9 are linked through an alkene divalent radical to form a cyclic ring, provided that at least one of R 20 -R 25 are divalent radicals, t1 and t2 independent of each other are integer number from 0 to 9, provided that (t1+t2) is an integer number from 2 to 9.