Polysiloxane-comprising perfluoroalkyl ethers and the preparation and use thereof
First Claim
1. A macromer of the formula (I)
where each P1, independently of the others, is a free-radical-polymerizable group;
each Y, independently of the others, is --CONHCOO--, --CONHCONH--, --OCONHCO--, --NHCONHCO--, --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--;
m and p, independently of one another, are 0 or 1;
each L, independently of the others, is a divalent radical of an organic compound having up to 20 carbon atoms;
each X1, independently of the others, is --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--; and
Q is a bivalent polymer fragment consisting of the segments(a) --(E)k --Z--CF2 --(OCF2)x --(OCF2 CF2)y --OCF2 --Z--(E)k --, where x+y is a number in the range from 10 to 30;
each Z, independently of the others, is a divalent radical having up to 12 carbon atoms or a bond;
each E, independently of the others, is --(OCH2 CH2)q, where q has a value of from 0 to 2, and where the link --Z--E-- represents the sequence --Z--(OCH2 CH2)q --; and
k is 0 or 1;
##STR4## where n is an integer from 5 to 100;
Alk is alkylene having up to 20 carbon atoms;
80-100% of the radicals R1, R2, R3 and R4, independently of one another, are alkyl and 0-20% of the radicals R1, R2, R3 and R4, independently of one another, are alkenyl, aryl or cyanoalkyl; and
(c) X2 --R--X2, where R is a divalent organic radical having up to 20 carbon atoms, and each X2, independently of the others, is --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--;
with the proviso that each segment (a) or (b) has a segment (c) attached to it; and
each segment (c) has a segment (a) or (b) attached to it.
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Accused Products
Abstract
The present invention describes a free radical polymerizable segmented macromonomer based on perfluoroelkyl ether, polysiloxane and divalent organic segments. This macromoner can be polymerized and used to form moldings, contact lenses, corneal implants and other biomedical articles.
212 Citations
68 Claims
- 1. A macromer of the formula (I)
- space="preserve" listing-type="equation">P.sub.1 --(Y).sub.m --(L--X.sub.1).sub.p --Q--(X.sub.1 --L).sub.p --(Y).sub.m --P.sub.1 (I)
where each P1, independently of the others, is a free-radical-polymerizable group;
each Y, independently of the others, is --CONHCOO--, --CONHCONH--, --OCONHCO--, --NHCONHCO--, --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--;
m and p, independently of one another, are 0 or 1;
each L, independently of the others, is a divalent radical of an organic compound having up to 20 carbon atoms;
each X1, independently of the others, is --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--; and
Q is a bivalent polymer fragment consisting of the segments(a) --(E)k --Z--CF2 --(OCF2)x --(OCF2 CF2)y --OCF2 --Z--(E)k --, where x+y is a number in the range from 10 to 30;
each Z, independently of the others, is a divalent radical having up to 12 carbon atoms or a bond;
each E, independently of the others, is --(OCH2 CH2)q, where q has a value of from 0 to 2, and where the link --Z--E-- represents the sequence --Z--(OCH2 CH2)q --; and
k is 0 or 1;
##STR4## where n is an integer from 5 to 100;
Alk is alkylene having up to 20 carbon atoms;
80-100% of the radicals R1, R2, R3 and R4, independently of one another, are alkyl and 0-20% of the radicals R1, R2, R3 and R4, independently of one another, are alkenyl, aryl or cyanoalkyl; and(c) X2 --R--X2, where R is a divalent organic radical having up to 20 carbon atoms, and each X2, independently of the others, is --NHCO--, --CONH--, --NHCONH--, --COO--, --OCO--, --NHCOO-- or --OCONH--; with the proviso that each segment (a) or (b) has a segment (c) attached to it; and
each segment (c) has a segment (a) or (b) attached to it.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68)
- 32. A polymer comprising a product of the polymerization of at least one compound of the formula (I) as defined in claim 1.
- 33. A polymer according to claim 32, wherein the proportion by weight of the compound of the formula (I) is in the range from 100 to 0.5%.
- 34. A polymer according to claim 32, which further comprises a vinylic comonomer (a).
- 35. A polymer according to claim 34, wherein the comonomer (a) is hydrophilic or hydrophobic or a mixture thereof.
- 36. A polymer according to claim 32, wherein the comonomer (a) is tristrimethylsilyloxysilylpropyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, tiimethylammonium 2-hydroxypropylmethacrylate hydrochloride, N,N-dimethylacrylamide or N-vinyl-2-pyrrolidone.
- 37. A crosslinked polymer comprising a product of the polymerization of at least one compound of the formula (1) as defined in claim 1 with at least one comonomer selected from the group consisting of a vinylic comonomer (a) and a polyunsaturated comonomer (b).
- 38. A polymer which comprises the polymerization product of the following components in weight percent based on the total weight of the polymer:
-
(1) 45-65% of a macromer according to claim 1, (2) 15-30% of a hydrophobic monomer, and (3) 10-35% of a hydrophilic monomer.
- 39. A polymer according to claim 38, comprising:
-
(1) 50-60% of a macromer according to claim 1, (2) 20-25% of a hydrophobic monomer, and (3) 15-30% of a hydrophlic monomer.
- 40. A polymer according to claim 38, comprising:
-
(1) 50-60% of a macromer of formula (1) according to claim 1, wherein P1 is, independently of the other, lower alkenyl, Y is, independently of the other, --COO-- or --OCO--, L is, independently of the other, lower alkylene, X1 is, independently of the other, --NHCOO-- or --OCONH--, p and m are 1;
the polymer fragment Q has up to 3 segments (a), up to 4 segments (b) and up to 6 segments (c), wherein in segment (a) the sum of the indices x+y is in the range of 10-15, Z is lower alkylene and k is 0, wherein in segment (b) Alk is lower alkylene, the radicals R1, R2, R3 and R4 are each independently of the others lower alkyl and n is in the range of 14-28, and wherein in segment (c) R is alkylene or arylene having up to 14 carbon atoms or a saturated divalent cycloaliphatic group having 6-14 carbon atoms, and X2 is --NHCOO-- or --OCONH--,(2) 20-25% of a hydrophobic monomer, and (3) 15-30% of a hydrophilic monomer.
- 41. A molding comprising a polymer according to claim 32.
- 42. A moulding according to claim 41, which is a contact lens.
- 43. A moulding according to claim 42, which is an intraocular lens.
- 44. A moulding according to claim 41 wherein the surface of the moulding is plasma treated in the presence of a C1 -C6 alkane (a) and a gas (b) which is selected from the group consisting of nitrogen, argon, oxygen, and mixtures thereof.
- 45. A moulding which comprises the polymer of a polymerization product of the following components in weight percent based on the total weight of the polymer:
-
(1) 45-65% of a macromer according to formula (I) of claim 1 wherein P1 is, independently of the other, lower alkenyl having up to 4 C-atoms, Y is, independently of the other, --COO-- or --OCO--, L is, independently of the other, lower alkylene having up to 4 carbon atoms, X1 is, independently of the other, --NHCOO-- or --OCONH--, p and m are 1;
the polymer fragment Q has one segment (a), up to 2 segments (b) and up to 2 segments (c), wherein in segment (a) the sum of the indices x+y is in the range of 10-15, Z is lower alkylene and k is 0, wherein in segment (b) Alk is lower alkylene having up to 4 carbon atoms, the radicals R1, R2, R3 and R4 are, each independently of the others, lower alkyl having up to 4 carbon atoms and n is in the range of 14-28, and wherein in segment (c) R is a saturated divalent cycloaliphatic group having 6-14 carbon atoms, and X2 is --NHCOO-- or --OCONH--,(2) 15-30% of a hydrophobic monomer, and (3) 10-35% of a hydrophilic monomer, wherein the surface of said moulding is plasma treated in the presence of a methane and air.
- 46. A biomedical article comprising a polymer according to claim 32.
- 47. A corneal implant comprising a polymer according to claim 32.
- 48. A corneal implant according to claim 47 which can be used in surgical implantation on or in the cornea of a mammal, where said implant has an optical property in the region over the optical axis which is suitable for impairing visual acuity, furthermore has a porosity which is sufficient to allow components of tissue fluid having a molecular weight of greater than 10,000 daltons to pass through, with flow of tissue fluid from cells outside the implant to cells inside the implant being ensured, and where the porosity in the region over the optical axis is arranged to such an extent that flow of components of tissue fluid is possible, but ingrowth of ocular tissue is excluded.
- 49. A corneal implant according to claim 47, where the implant is coated with one or more components which promote growth of tissue in the vicinity of the implant and/or promote cell adhesion to the implant.
- 50. A corneal implant according to claim 47, where the porosity of the implant is provided by a multiplicity of pores whose size is sufficient to ensure flow of protein components of tissue fluid having a molecular weight of more than 10,000 daltons through the implant, but whose pore size excludes ingrowth of tissue.
- 51. A corneal implant according to claim 49, where the majority of the pores have a diameter of from 15 nanometers to 0.5 microns.
- 52. A cell-growth substrate comprising a polymer according to claim 32.
- 53. A medical implant comprising a polymer according to claim 32.
- 54. A macromer according to claim 4, in which the mean molecular weight of the polymer fragment Q is in the range from about 3000 to about 15,000.
- 55. A macromer according to claim 54, in which the mean molecular weight of the polymer fragment Q is in the range from about 5000 to about 12,000.
- 56. A macromer according to claim 5, in which the total number of segments (a) and (b) in the polymer fragment Q is in the range from 2 to about 9.
- 57. A macromer according to claim 56, in which the total number of segments (a) and (b) in the polymer fragment Q is in the range from 2 to about 7.
- 58. A macromer according to claim 12, in which the indices x+y are a number in the range from 10 to 15.
- 59. A macromer according to claim 13, in which the ratio x:
- y is in the range from 0.7 to 1.1.
- 60. A macromer according to claim 15, in which P1 is alkenyl or alkenylaryl having up to 8 carbon atoms.
- 61. A macromer according to claim 60, in which P1 is alkenyl or alkenylaryl having up to 4 carbon atoms.
- 62. A macromer according to claim 23, in which n is an integer from 10 to 50.
- 63. A macromer according to claim 62, in which n is an integer from 14 to 28.
- 64. A macromer according to claim 24, in which 90-100% of the radicals R1 R2, R3 and R4, independently of one another, are lower alkyl having up to 4 carbon atoms.
- 65. A polymer according to claim 33, wherein the proportion by weight of the compound of the formula (I) is in the range from 80 to 10%.
- 66. A polymer according to claim 65, wherein the proportion by weight of the compound of the formula (I) is in the range from 70 to 30%.
- 67. An article having a surface coating which comprises a macromer of formula (I) of claim 1.
- 68. An article having a surface coating which comprises a polymer of claim 32.
Specification