Organic polymers

Details Organic polymers Organic polymers

1999-12-21

2002-09-03

Moore, Margaret G. (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From silicon reactant having at least one...

C528S028000, C528S059000, C528S068000, C528S085000, C528S076000, C528S077000, C528S337000, C528S342000, C528S345000, C528S364000, C528S367000, C523S106000, C523S107000, C264S331110, C264S331180, C264S331150, C264S331160

Reexamination Certificate

active

06444776

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. No. 5,807,944 discloses crosslinkable amphiphilic block copolymers comprising a hydrophobic polysiloxane middle block to which are linked two polyoxazoline blocks via an alkylene bridge member. According to the present invention there are provided—by means of an alternative synthetic route—novel crosslinkable block copolymers comprising a hydrophobic block and one or more polyoxazoline blocks that are linked to the hydrophobic block via specific functional groups. Said novel synthetic route allows to design specific crosslinkable amphiphilic block copolymers with further improved properties which are particularly useful in the manufacture of ophthalmic mouldings such as contact lenses.
The present invention thus in one aspect relates to an amphiphilic block copolymer of formula
wherein
A is a hydrophobic segment selected from the group consisting of a polysiloxane, a perfluoroalkyl polyether; a polymer of a conjugated aliphatic or alicyclic diene, a polymer of an alkyne or dialkyne, an optionally partially hydrated copolymer of a conjugated diene and a hydrophilic or hydrophobic vinylic monomer, and a polysulfone;
B is a hydrophilic segment of formula
wherein R
1
is hydrogen, C
1
-C
12
-alkyl or C
3
-C
12
-alkenyl which is in each case unsubstituted or substituted by hydroxy or fluoro and/or uninterrupted or interrupted by oxygen, an ester and/or an urethane group, or is C
5
-C
8
-cycloalkyl, phenyl or benzyl, R is C
1
-C
12
-alkylene, C
7
-C
12
-aralkylene or unsubstituted or C
1
-C
4
-alkyl-substituted phenylene, Q
1
and Q
2
are each independently of the other an organic radical that comprises at least one crosslinkable group or, if R
1
comprises an alkenyl group, may also be C
1
-C
2
-alkyl or benzyl, X is a group —O—, —S—, —NR′— or —N(R′)
2
+
—An
−
wherein R′ is hydrogen or C
1
-C
4
-alkyl and An
−
is an anion, and p is an integer from 2 to 150;
L is a bivalent linking group of formula
—X
1
—R
2
—X
2
—  (3a),
—X
1
—C(O)—NH—R
2
—NH—C(O)—X
2
—  (3b),
—X
1
—C(O)—R
2
—C(O)—X
2
—  (3c),
—X
1
—C(O)—(R*)
c
—  (3d),
—C(O)—X
1
—  (3e), or
—X
1
—C(O) X
2
—  (3f),
wherein X
1
and X
2
are each independently of the other a group —O—, —S— or —NR
0
—, R
0
is hydrogen or C
1
-C
4
-alkyl, R
2
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
-
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
-
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, R* is C
1
-C
4
-alkylene or benzylene, c is 1 if B is a radical of formula (2) and is 0 if B is a radical of formula (2a);
and n is an integer ≧1.
Preferred hydrophobic segments A comprise a perfluoroalkyl polyether or particularly a polysiloxane.
According to one preferred embodiment of the invention, the segment A comprises a polysiloxane block having terminal alkylene groups of formula
in which m is an integer from 5 to 700; Alk is alkylene having up to 20 carbon atoms which may be interrupted by —O—; 80-100% of the radicals R
3
, R
4
, R
5
and R
6
, independently of one another, are C
1
-C
8
-alkyl and 0-20% of the radicals R
3
, R
4
, R
5
and R
6
, independently of one another, are C
3
-C
12
-alkenyl, unsubsttituted 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).
In a preferred meaning, m is an integer from 10 to 500, more preferably 10 to 300, particularly preferably 20 to 150 and in particular 50 to 140.
In a preferred meaning, 80-100%, preferably 85-100%, in particular 90-100%, of the radicals R
3
, R
4
, R
5
and R
6
, are, independently of one another, alkyl having up to 6 carbon atoms, particularly preferably alkyl having up to 4 carbon atoms, especially alkyl having up to 2 carbon atoms. A further particularly preferred meaning of R
3
, R
4
, R
5
and R
6
is methyl.
In a preferred meaning, 0-20%, preferably 0-15%, in particular 0-10%, of the R
3
, R
4
, R
5
and R
6
are, independently of one another, C
3
-C
8
-alkenyl, unsubstituted or C
1
-C
2
-alkyl- or C
1
-C
2
-alkoxy-substituted phenyl, fluoro(C
1
-C
8
-alkyl), e.g., trifluoropropyl, or cyano(C
1
-C
4
-alkyl).
According to another embodiment of the invention, the oxygen-permeable polymer in segment A comprises a perfluoroalkyl-polyether block of Formula (II)
—(E)
k
—Z—CF
2
—(OCF
2
)
x
—(OCF
2
CF
2
)
y
—OCF
2
—Z—(E)
k
  (5)
in which x+y 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
)
q
, where q 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
)
q
—; 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 x and y in Formula (5) can have a random distribution. The sum of the indices x+y is preferably a number in the range from 10 to 50, particularly preferably from 10 to 30. The ratio x:y is preferably in the range from 0.5 to 1.5, in particular in the range from 0.8 to 1.2.
In another embodiment of the invention, the segment A comprises an unsaturated polymer, e.g., a polymer of a conjugated aliphatic or alicyclic diene, which may be substituted by halogen or C
1
-C
6
-alkyl, a polymer of an alkyne or dialkyne, which may be substituted by C
1
-C
6
-alkyl or trimethylsilyl, a copolymer of a conjugated diene and a hydrophilic or hydrophobic vinylic monomer, or a partially hydrated derivatives of the mentioned compounds.
Specific examples of preferred unsaturated polymers are cis-, trans, iso- or syndiotactic poly-1,2-butadiene, poly-1,4-butadiene or polyisoprene; poly-pentenamer; polychloroprene; polypiperylen; butadiene- or isoprene-copolymers with hydrophilic or hydrophobic vinylic monomers, such as acrylonitrile, styrene, acrylic acid or hydroxyethylmethacrylate; or poly-1-trimethylsilyl-propyne. An especially preferred unsaturated polymer is selected from syndiotactic poly-1,2-butadiene, poly-1,4-butadiene and polyisoprene. An especially preferred unsaturated polymer is poly-1-trimethylsilyl-propyne. Another especially preferred unsaturated polymer is poly-1,4-butadiene.
In a further embodiment of the invention, the segment A comprises a polysulfone comprising at least one of the structural elements (6a) to (6d)
 —R
7
—SO
2
—R
7
—O—  (6c), or
—R
7
—O—R
7
—SO
2
—R
7
—R
7
—SO
2
—  (6d)
wherein R
7
in structural element (6a) is C
1
-C
8
-alkylene or C
6
-C
14
-arylene, in particular C
1
-C
4
-alkylene or phenylene, and R
7
in structural elements (6b), (6c) and (6d) is C
6
-C
14
-arylene, especially phenylene.
In one embodiment of the invention, the segment A may comprise one of the polymers illustrated above. 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 or polybutadiene subsegments (a) and polysiloxane subsegments (b).
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.
Regarding the hydrophilic blocks of formula (2) or (2a), R
1
is preferably C
1
-C
8
-alkyl which is unsubstituted or substituted by hydroxy or fluorine and/or is un

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