High water content porous polymer

• US 6,160,030 A
• Filed: 03/25/1999
• Issued: 12/12/2000
• Est. Priority Date: 04/04/1996
• Status: Expired due to Term

• Current Assignee: Novartis Ag
• Original Assignee: Novartis Ag
• Inventors: Chaouk, Hassan, Meijs, Gordon Francis
• Primary Examiner(s): COONEY, JOHN M
• Application Number:
  US09/155,551
• Time in Patent Office: 628 Days
• Field of Search: 521/63, 521/64, 521/88, 521/144, 521/145, 521/149, 521/154
• US Class Current: 521/145
• CPC Class Codes: B01D 2323/18 Pore-control agents or pore formers
• CPC Class Codes: B01D 2325/02 Details relating to pores or porosity of the membranes
• CPC Class Codes: B01D 2325/026 Sponge structure
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 2325/22 Thermal or heat-resistance properties
• CPC Class Codes: B01D 2325/28 Degradation or stability over time
• CPC Class Codes: B01D 2325/30 Chemical resistance
• CPC Class Codes: B01D 67/0006 by chemical reactions in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125
• CPC Class Codes: B01D 67/003 by selective elimination of components, e.g. by leaching
• CPC Class Codes: B01D 71/32 containing fluorine atoms
• CPC Class Codes: C08G 65/007 containing fluorine
• CPC Class Codes: C08J 2371/00 Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08J2359/00; of epoxy resins C08J2363/00; of polythioether-ethers C08J2381/02; of polyethersulfones C08J2381/06; Derivatives of such polymers
• CPC Class Codes: C08J 9/286 the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The present invention relates to porous polymers comprising a perfluoropolyether unit, to a process for producing such porous polymers, in particular to a process for polymerising or copolymerising monomers incorporating perfluoropolyethers to form porous polymers, to articles made of or comprising porous polymers comprising a perfluoropolyether unit, such as membranes or ophthalmic devices, and to the use of porous polymers comprising perfluoropolyether units as articles, such as membranes or ophthalmic devices. The perfluoropolyether units are preferably of the formula (PFPE):--OCH₂ CF₂ O(CF₂ CF₂ O)_x (CF₂ O)_y CF₂ CH₂ O-- wherein the CF₂ CF₂ O and CF₂ O units may be randomly distributed or distributed as blocks throughout the chain and wherein x and y may be the same or different such that the molecular weight of the perfluorinated polyether is in the range of from 242 to 4,000. The porous polymers comprising one or more perfluoropolyether units having a water content when fully swollen in water which is higher than that of the same polymer if polymerized under conventional conditions, and are suitable for application, e.g., as soft contact lenses.

Claims

1. A porous polymer polymerized from monomers comprising macromonomers having one or more perfluoropolyether units, and using porogens during polymerization,

wherein polymerization starts from a co-continuous microemulsion and displays a discrete phase during or at the end of polymerization, the discrete phase forming a interpenetrating network, and

wherein the water contents of the polymer, when fully equilibrated with water, is above 5 weight percent.

3. A porous polymer according to claim 1 wherein the perfluoropolyether units are of formula PFPE

4. A porous polymer according to claim 1 wherein the macromonomer is of formula (I):

space="preserve" listing-type="equation">Q-(PFPE-L).sub.n-1 -PFPE-Q (I)

wherein

Q may be the same or different and is a polymerizable group,

PFPE is a moiety of formula PFPE;

space="preserve" listing-type="equation">--OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2).sub.x (CF.sub.2 O).sub.y CF.sub.2 CH.sub.2 O-- (PFPE)

wherein the CF₂ CF₂ O and CF₂ 0 units may be randomly distributed or distributed as blocks throughout the chain and wherein x and y may be the same or different such that the molecular weight of the perfluorinated polyether is in the range of from 242 to 4,000,

L is a difunctional linking group; and

n is at least 1.

5. A porous polymer according to claim 1 wherein the macromonomer is of formula (II):

space="preserve" listing-type="equation">Q-B-(L-B)n-T (II)

wherein

Q may be the same or different and is a polymerizable group,

L is a difunctional linking group;

n is at least 1;

each B may be the same or different and is a difunctional block of molecular weight in the range of from 100 to 4000 and wherein at least one B is a perfluorinated polyether of formula (PFPE);

PFPE is a moiety of formula PFPE;

space="preserve" listing-type="equation">--OCH.sub.2 CF.sub.2 O (CF.sub.2 CF.sub.2).sub.x (CF.sub.2 O).sub.y CF.sub.2 CH.sub.2 O-- (PFPE)

wherein the CF₂ CF₂ O and CF₂ O units may be randomly distributed or distributed as block(s throughout the chain and wherein x and y may be the same or different such that the molecular weight of the perfluorinated polyether is in the range of from 242 to 4,000, and T is a univalent terminal group which is not polymerisable by free radicals but which may contain other functionality.

6. A porous polymer according to claim 1 wherein the macromonomer is of formula (III)

7. An article comprising a porous polymer as claimed in claim 1.

8. An article according to claim 7 which is an ophthalmic device.

9. An article according to claim 8 which is a contact lens.

10. An article according to claim 7 which is a membrane.

11. A process for the production of a porous polymer of claim 1 comprising the steps of:

i) forming a mixture comprising a polymerizable component and an organic solvent wherein the polymerizable component comprises at least one macromonomer having at least one perfluoropolyether unit;

ii) polymerizing said mixture wherein immediately after the polymerization of said mixture at least a substantial proportion of said organic solvent is in the form of a discrete phase arid wherein said discrete organic solvent phase forms an interpenetrating network throughout the mixture or is dispersed throughout the mixture; and

iii) removing the discrete organic solvent phase.

12. A process according to claim 11 wherein the organic solvent is diisopropyl ether.

13. A process for producing a porous polymer of claim 1 comprising the steps of:

1) dispersing a porogen in a continuous monomer component phase wherein said continuous monomer component phase comprises at least one monomer having at least one perfluoropolyether unit and wherein said porogen is an optionally substituted poly(alkylene)glycol;

2) thereafter polymerising the continuous monomer phase; and

3) removing the porogen from the porous polymer.

14. A process according to claim 13 wherein the porogen is polypropylene glycol.

15. An article comprising a porous polymer obtainable according to the process of claim 11.

16. An article comprising a porous polymer obtainable according to the process of claim 13.

17. An article according to claim 15 which is a contact lens.

18. An article according to claim 16 which is a contact lens.

2. A polymer manufactured from monomers comprising macromonomers having one or more perfluoropolyether units polymerized in a solvent which forms a homogeneous solution with the monomer components,

wherein the solution displays a discrete phase during or at the end of polymerization, the discrete phase forming a interpenetrating network, and

wherein the water contents of the polymer, when fully equilibrated with water, is above 5 weight percent.