Organic polymers

Details Organic polymers Organic polymers

2000-07-28

2004-04-06

Dawson, Robert (Department: 1712)

Optics: eye examining, vision testing and correcting

Spectacles and eyeglasses

Ophthalmic lenses or blanks

C523S107000, C264S299000, C264S001320, C528S033000, C528S026000, C528S029000, C528S025000, C528S376000, C528S030000, C568S615000, C525S479000

Reexamination Certificate

active

06715874

ABSTRACT:

The present invention relates to novel crosslinkable copolymers, to a process for the preparation thereof and to the use thereof for the manufacture of mouldings, especially ophthalmic mouldings.
U.S. Pat. Nos. 5,760,100 or 5,807,944 disclose crosslinkable amphiphilic block copolymers comprising a hydrophobic middle block to which are linked two or more hydrophilic blocks. While the materials disclosed therein in general have proven to be effective as bulk material for the manufacture of biomedical articles, the availability, chemical constitution and size of suitable hydrophilic blocks as well as the further processing of the known block copolymers is often problematic. In particular, the control of the segmental length of the hydrophilic segments is often difficult. Therefore, it would be highly desirable to provide more easily accessible hydrophilic blocks of variable chain length having a single functional group undergoing coupling with the hydrophobic segment and one or more different functional groups useful to attach a polymerizable moiety. Such hydrophilic blocks would allow to design specific crosslinkable amphiphilic block copolymers with specific polymer and segmental architectures depending on the desired use. In addition, a simplified manufacture of mouldings from such amphiphilic block copolymers would be desirable which omits time consuming steps such as, for example, the removal of extractables, that are unpolymerized components or compounds that are not firmly anchored in the polymer network, after the polymerization or crosslinking step.
Therefore, it is an object of the invention to provide novel crosslinkable amphiphilic block copolymers, within the application also called prepolymers, which are based on easily accessible hydrophilic blocks with high variability of chemical constitution and segmenral length, and which make it possible to manufacture mouldings, in particular biomedical mouldings such as especially ophthalmic mouldings, in a very efficient manner.
The present invention therefore in one aspect relates to a crosslinkable amphiphilic block copolymer of formula
wherein A is a hydrophobic segment selected from the group consisting of a polysiloxane, a perfluoroalkyl polyether and mixtures thereof,
L is is a bivalent linking group of formula
—X
1
—C(O)—NH—R—NH—C(O)—X
2
—  (2a),
—X
1
—C(O)—R—C(O)—X
2
—  (2b),
—C(O)—X
2
—  (2c),
—X
1
—C(O)—  (2d) or
—X
1
—C(O)—X
2
—  (2e),
 wherein X
1
and X
2
are each independently of the other a group —O—, —S— or —NR
1
—, R
1
is hydrogen or C
1
-C
4
-alkyl, R is linear or branched C
1
-C
18
-alkylene or unsubstituted or C
1
-C
4
-alkyl- or C
1
-C
4
-alkoxy-substituted C
6
-C
10
-arylene, C
7
-C
18
-aralkylene, C
6
-C
10
-arylene-C
1
-C
2
-alkylene-C
6
-C
10
-arylene, C
3
-C
8
-cycloalkylene, C
3
-C
8
-cycloalkylene-C
1
-C
6
-alkylene, C
3
-C
8
-cycloalkylene-C
1
-C
2
-alkylene-C
3
-C
8
-cycloalkylene or C
1
-C
6
-alkylene-C
3
-C
8
-cycloalkylene-C
1
-C
6
-alkylene;
(alk) is C
2
-C
12
-alkylene;
(oligomer) is the radical of a hydrophilic telomer which is derived from one or more different copolymerizable vinyl monomers;
Q is an organic radical comprising at least one crosslinkable or polymerizable group;
m is an integer from 1 to 4, and n is an integer ≧1.
According to one preferred embodiment of the invention, the segment A comprises a polysiloxane block having terminal alkylene groups of formula
in which (alk′) is alkylene having up to 20 carbon atoms which may be interrupted by —O—; 80-100% of the radicals R
2
, R
2
′, R
2
″, R
2
′″, R
2
*, R
3
, R
3
′ and R
3
″, independently of one another C
1
-C
8
-alkyl and 0-20% of the radicals R
2
, R
2
′, R
2
″, R
2
′″, R
2
*, R
3
, R
3
′ and R
3
″, independently of one another, are C
3
-C
12
-alkenyl, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
-alkoxy-substituted phenyl, fluoro(C
1
-C
18
-alkyl) or cyano(C
1
-C
12
-alkyl), x is 0 or 1, d
1
is an integer of from 5 to 700, d
2
is (n−2) if x is 0, and is n if x is 1 wherein n is as defined above, and the sum of (d
1
+d
2
) is from 5 to 700.
In a preferred meaning, the sum of (d
1
+d
2
) is an integer from 10 to 500, more preferably 10 to 300, particularly preferably 20 to 200 and in particular 25 to 150.
(alk′) is preferably C
2
-C
8
-alkylene, which may be interrupted by —O— and more preferably C
2
-C
6
-alkylene which may be interrupted by —O—. Examples of particular preferred radicals (alk′) are linear or branched C
2
-C
6
alkylene or a radical —(CH
2
)
1-3
—O—(CH
2
)
1-3
—, especially C
2
-C
4
-alkylene or a radical —(CH
2
)
2-3
—O—(CH
2
)
2-3
—.
Preferably the radicals R
2
, R
2
′, R
2
″, R
2
′″, R
2
*, R
3
, R
3
′ and R
3
″ are each independently another C
1
-C
6
-alkyl, more preferably each C
1
-C
4
-alkyl, more preferably each C
1
-C
2
-alkyl and in particular each methyl.
One embodiment of suitable polysiloxane hydrophobic blocks (A) emcompasses a radical of the above formula (3), wherein x is 0, d
2
is 0, d
1
is an integer from 5 to 700, preferably 10 to 500, more preferably 10 to 300, even more preferably 20 to 200 and in particular preferably 25 to 150, R
2
, R
2
′, R
2
″, R
2
′″, R
2
*, R
3
, R
3
′ and R
3
″ are each independently of one another C
1
-C
6
-alkyl and for (alk′) the above given meanings and preferences apply.
Another embodiment of suitable polysiloxane hydrophobic blocks (A) emcompasses a radical of the above formula (3), wherein x is 0, d
2
is the sum of (n−2) and is ≧1, and for R
2
, R
2
′, R
2
″, R
2
′″, R
2
*, R
3
, R
3
′ and R
3
″, d
1
and (alk′) the above-given meanings and preferences each apply.
Still another embodiment of suitable polysiloxane hydrophobic blocks (A) emcompasses a radical of the above formula (3), wherein x is 1, d
2
is equivalent to n, and for R
2
, R
2
′, R
2
″, R
2
′″, R
2
*, R
3
, R
3
′, d
1
and R
3
″ each the above-given meanings and preferences each apply.
According to another embodiment of the invention, the oxygen-permeable polymer in segment A comprises a perfluoroalkyl-polyether block of formula
—(E)
k
—Z—CF
2
—(OCF
2
)
b1
—(OCF
2
CF
2
)
b2
—OCF
2
—Z—(E)
k
  (4)
in which (b1+b2) is a number in the range from 10 to 100; 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 alkoxy, e.g. —(OCH
2
CH
2
)
a
—, where a has a value of from 0 to 2 as a statistical average, and where the link —Z—E— represents the sequence —Z—(OCH
2
CH
2
)
a
—; and k is 0 or 1.
Z is preferably a bond, C
1-C
8
-alkylene or —CONH-phenylene, in which the —CO— moiety is linked to a CF
2
group. Z is particularly preferably C
1
-C
4
-alkylene, in particular methylene.
The perfluoroalkoxy units OCF
2
and OCF
2
CF
2
having the indices b1 and b2 in Formula (4) can have a random distribution. The sum of the indices (b1+b2) is preferably a number in the range from 10 to 50, particularly preferably from 10 to 30. The ratio b1:b2 is preferably in the range from 0.5 to 1.5, in particular in the range from 0.8 to 1.2.
In one embodiment of the invention, the segment A may comprise one of the polymers illustrated above, in particular a polysiloxane. According to another embodiment, the polymer in segment A may comprise more than one kind of polymers as illustrated above, e.g., may comprise perfluoroalkylene polyether subsegments and polysiloxane subsegments.
Segments A of the prepolymers of the invention have a mean molecular weight of for example in the range from about 1,000 to about 50,000, preferably in the range from about 1,500 to about 30000 and particularly preferably in the range from about 2,000 to about 20,000.
The linking groups L of formulae (2a)-(2e) are to be understood that the left bond is directed to A and the right bond is directed to (alk).
I

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