Crosslinkable prepolymers from a hydrophilic monomer and a hydrophobic crosslinker

• US 7,091,283 B2
• Filed: 03/23/2001
• Issued: 08/15/2006
• Est. Priority Date: 03/24/2000
• Status: Expired due to Term

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Müller, Beat, Laurent, Alain, Molenberg, Aaldert Rens, Coessens, Veerle
• Primary Examiner(s): Lipman, Bernard
• Application Number:
  US09/815,674
• Publication Number:
  US 20010037001A1
• Time in Patent Office: 1,971 Days
• Field of Search: 525/292, 526/211, 526/214, 526/220
• US Class Current: 525/292
• CPC Class Codes: C08F 2/48 by ultraviolet or visible light
• CPC Class Codes: C08F 255/00 Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/10 on to polymers of amides or imides
• CPC Class Codes: C08F 271/00 Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
• CPC Class Codes: C08F 283/06 on to polyethers, polyoxymethylenes or polyacetals C08F283/004 takes precedence
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 290/00 Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• CPC Class Codes: C08F 290/04 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C08F 290/14 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/142 Polyethers
• CPC Class Codes: C08F 290/148 Polysiloxanes
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08G 77/26 : nitrogen-containing groups
• CPC Class Codes: C08G 77/46 : containing polyether sequences
• CPC Class Codes: C08G 77/70 : Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08L 2666/02 : Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/00 : Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds for ABS polymers C08L55/02; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 51/003 : grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 51/08 : grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 51/085 : on to polysiloxanes
• CPC Class Codes: C08L 53/00 : Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 : Polysiloxanes
• CPC Class Codes: G02B 1/043 : Contact lenses

Abstract

The invention relates to novel crosslinkable copolymers which are obtainable by (a) copolymerizing at least one hydrophilic monomer having one ethylenically unsaturated double bond and at least one crosslinker comprising two or more ethylenically unsaturated double bonds in the presence of a chain transfer agent having a functional group; and (b) reacting one or more functional groups of the resulting copolymer with an organic compound having an ethylenically unsaturated group. The crosslinkable copolymers of the invention are especially useful for the manufacture of biomedical mouldings, for example ophthalmic mouldings such as in particular contact lenses.

Claims

1. A crosslinkable or polymerizable prepolymer that is obtained by

(a) copolymerizing at least one hydrophilic monomer having one first ethylenically unsaturated group and at least one crosslinker comprising two or more second ethylenically unsaturated groups in the presence of a chain transfer agent comprising a chain transfer group and a first reactive group to obtain a copolymerization product with first reactive groups, wherein said at least one crosslinker is a polysiloxane, a perfluoroalkyl polyether, or a polysiloxane/perfluoroalkyl polyether block copolymer, wherein the hydrophilic monomer is a monomer which, when polymerized, gives a homopolymer which is water-soluble or can absorb at least 10% by weight of water;

and

(b) reacting an organic compound with the copolymerization product to form the crosslinkable or polymerizable prepolymer having third ethylenically unsaturated groups, wherein the organic compound comprises a third ethylenically unsaturated group and a second reactive group, wherein the second reactive group of the organic compound reacts with one of the first reactive groups of the copolymerization product,

wherein said crosslinkable or polymerizable prepolymer can be crosslinked or polymerized to form a polymeric material capable of forming a hydrogel when contacted with water.

2. A prepolymer according to claim 1, wherein the hydrophilic monomer according to step (a) is a radical of formula

3. A prepolymer according to claim 1, wherein the hydrophilic monomer according to step (a) is a radical of formula

4. A prepolymer according to claim 1, wherein the crosslinker according to step (a) is a polysiloxane of formula

5. A prepolymer according to claim 1, wherein the crosslinker according to step

(a) is a polysiloxane of formula

6. A prepolymer according to claim 1, wherein the functional chain transfer agent used in step (a) is an organic primary thiol having a hydroxy, amino, N—

C₁–

C₆-alkylamino or carboxy group.

7. A prepolymer according to claim 1, wherein, the components in step (a) are used in a molar ratio of from 0.5 to 5 equivalents chain transfer agent:

1 equivalent crosslinker;

5 to 60 equivalents hydrophilic monomer(s).

8. A prepolymer according to claim 1, wherein the organic compound is described by formula

9. A prepolymer according to claim 1, wherein the crosslinker is a perfluoroalkyl polyether of formula

Q-(PFPE-L)_n-1-PFPE-Q 

 

(5),

wherein n is ≧

1, each PFPE may be the same or different and is a perfluorinated polyether of formula

—

OCH₂CF₂O(CF₂CF₂O)_z(CF₂O)_yCF₂CH₂O—

 

 

(6)

wherein the CF₂CF₂O and CF₂O units may be randomly distributed or distributed as blocks throughout the chain and wherein z and y may be the same or different such that the weight average molecular weight of the perfluoropolyether is in the range of from 500 to 4,000;

wherein L is a difunctional linking group; and

wherein Q is an organic radical comprising a crosslinkable or polymerizable group.

10. A prepolymer according to claim 1, wherein the crosslinker is a macromonomer of the formula (5a)

Q-PFPE-Q 

 

(5a)

wherein Q is an organic radical comprising a crosslinkable or polymerizable group;

PFPE is a perfluorinated polyether of formula (6)

—

OCH₂CF₂O(CF₂CF₂O)_z(CF₂O)_yCF₂CH₂O—

 

 

(6)

wherein z and y may be the same or different such that the molecular weight of the perfluoroalkyl polyether is in the range of from 500 to 2,500.

11. A prepolymer according to claim 1, wherein the crosslinker is a polysiloxane/perfluoroalkyl polyether block copolymer of the formula

Q-PFPE-L-M-L-PFPE-Q 

 

(7)

wherein

L is a difunctional linking group;

Q is an organic radical comprising a crosslinkable or polymerizable group;

PFPE is a perfluorinated polyether of formula (6)

—

OCH₂CF₂O(CF₂CF₂O)_z(CF₂O)_yCF₂CH₂O—

 

 

(6)

 

in which z and y may be the same or different such that the molecular weight of the perfluoroalkyl polyether is in the range of from 500 to 2,500; and

M is a radical of formula (2b)

12. A prepolymer according to claim 1, wherein the crosslinker is a polysiloxane of formula (2c)

Q-(PDMS)₁-L-(PDMS)₂-Q 

 

(2c),

wherein

(PDMS)₁ and (PDMS)₂ are, each, independently of the other, a radical of formula (2b)