Polymers containing zwitterionic monomers

Details Polymers containing zwitterionic monomers Polymers containing zwitterionic monomers

1999-07-12

2004-01-06

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S278000, C526S310000, C526S312000, C526S328000, C526S328500, C427S372200, C427S383100, C427S387000, C427S388500

Reexamination Certificate

active

06673883

ABSTRACT:

This invention relates to new polymeric materials especially suitable for use in biomedical applications, and processes for their production and use.
According to the present invention there is provided a crosslinkable polymer formed from monomers including
a) a hydroxyl-group containing monomer of the general formula I
in which R
26
is hydrogen or C
1-4
-alkyl group A
1
is —O— or —NR
27
— where R
27
is hydrogen or a C
1-4
-alkyl group or a group B
9
R—(OH)
n
;
B
9
is a bond, a straight or branched alkylene, a oxa alkylene or oligooxa alkylene group;
R
13
is a n+1 functional (optionally substituted) C
1-24
alkylene group,
n is an integer of one or more; and
b) a reactive monomer of the general formula (II)
in which R
19
is hydrogen or a C
1-4
-alkyl group or A
2
is —O— or —NR
21
— where R
21
is hydrogen, or a C
1-4
-alkyl group R
12
is C
1-24
straight or branched alkylene, oxaalkylene or oligo oxaalkylene group in which each alkylene group has 1 to 6 carbon atoms
A
3
is a band or —O—
each R
16
independently selected from C
1-6
-alkyl groups.
In hydroxyl group containing monomer of the general formula I, R
26
is preferably hydrogen or methyl, most preferably methyl. A
1
is preferably —O—. B
9
is preferably a bond.
R
13
is preferably selected from C
2-6
-alkylene groups, most preferably C
2-4
-alkylene, most preferably propylene. The monomer I may consist of a mixture of compounds having different groups R
13
. Preferably, in such a mixture, all groups R
13
have the same number of carbon atoms, but may comprise a mixture of different isomers. For instance where the group R
13
is propylene, it may consist of a mixture of 1,2-propylene and 1,3-propylene.
In the reactive monomer of the general formula II, R
19
is preferably selected from hydrogen and methyl groups, most preferably R
19
is methyl. A
2
is preferably —O—. A
3
is preferably —O—. R
12
is preferably C
2-6
-alkylene, preferably C
2-4
-alkylene. Again, the monomer of the formula II may comprise a mixture of compounds having different groups R
12
.
R
16
is selected from C
1-6
-alkyl groups, preferably C
1-2
-alkyl groups.
Preferred polymers are made from monomers including a zwitterionic monomer of the general formula III
wherein B is a straight or branched alkylene, oxaalkylene or oligo-oxaalkylene chain optionally containing one or more fluorine atoms up to and including perfluorinated chains or, if X contains a carbon—carbon chain between B and the zwitterionic moiety or if Y contains a terminal carbon atom bonded to B, a valence bond;
X is a zwitterionic group
R is hydrogen or a C
1
-C
4
alkyl group; and
A is —O— or —NR
1
— where R
1
is hydrogen or a C
1
-C
4
alkyl group or R
1
is —B—X where B and X are as defined above.
In compounds of formula (III) it is preferred that K and B contain up to 12 carbon atoms in total.
In the zwitterionic monomer of the general formula III, R is preferably selected from hydrogen and methyl, and is most preferably methyl.
Preferably B
9
is an alkylene group of formula —(CR
3
2
)
a
—, wherein the groups —(CR
3
2
)— are the same or different, and in each group —(CR
3
2
)— the groups R
3
are the same or different and each group R
3
is hydrogen, fluorine or C
1-4
alkyl or fluoroalkyl, preferably hydrogen, and a is from 1 to 12, preferably 1 to 6;
an oxaalkylene group such as alkoxyalkyl having 1 to 6 carbon atoms in each alkyl moiety, more preferably —CH
2
O(CH
2
)
4
—; or
an oligo-oxaalkylene group of formula —[(CR
4
2
)
b
O]
c
(CR
4
2
)
b
— where the groups —(CR
4
2
)— are the same or different and in each group —(CR
4
2
)— the groups R
4
are the same or different and each group R
4
is hydrogen, fluorine or C
1-4
alkyl or fluoroalkyl, preferably hydrogen, and b is from 1 to 6, preferably 2 or 3 and c is from 2 to 11, preferably 2 to 5; or
if X contains a carbon—carbon chain between B and the centre of permanent positive charge or if Y contains a terminal carbon atom, a valence bond.
Preferred groups B include alkylene, oxaalkylene and oligo-oxaalkylene groups of up to 12 carbon atoms optionally containing one or more fluorine atoms.
Preferred zwitterionic groups on zwitterionic monomer III are groups in which the cationic moiety is based on a quaternary ammonium group and the anionic moiety is based on a phosphate group. Preferred zwitterionic groups are ammonium phosphate ester zwitterionic groups. Preferably the ammonium is quaternary ammonium and the phosphate group is a diester group, or amide analogue. Usually the cationic group is located at the end of pendant group X distant from B.
Preferably X is a group of formula
in which the moieties X
1
and X
2
, which are the same or different, are —O—, —S—, —NH— or a valence bond, preferably —O—, and W
+
is a group comprising an ammonium, phosphonium or sulphonium cationic group and a group linking the anionic and cationic moieties which is preferably a C
1-12
-alkylene group.
Preferably W contains as cationic group an ammonium group, more preferably a quaternary ammonium group.
The group W
+
may for example be a group of formula
—W
1
—N
+
R
23
3
, —W
1
—P
+
R
23a
3
, —W
1
—S
+
R
23a
2
or —W
1
-Het
+
in which:
W
1
is alkylene of 1 or more, preferably 2-6 carbon atoms optionally containing one or more ethylenically unsaturated double or triple bonds, disubstituted-aryl, alkylene aryl, aryl alkylene, or alkylene aryl alkylene, disubstituted cycloalkyl, alkylene cycloalkyl, cycloalkyl alkylene or alkylene cycloalkyl alkylene, which group W
1
optionally contains one or more fluorine substituents and/or one or more functional groups; and either
the groups R
23
are the same or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, preferably methyl, or aryl, such as phenyl or two of the groups R
23
together with the nitrogen atom to which they are attached form a heterocyclic ring containing from 5 to 7 atoms or the three groups R
23
together with the nitrogen atom to which they are attached form a fused ring structure containing from 5 to 7 atoms in each ring, and optionally one or more of the groups R
23
is substituted by a hydrophilic functional group, and
the groups R
23a
are the same or different and each is R
23
or a group OR
23
, where R
23
is as defined above; or
Het is an aromatic nitrogen-, phosphorus- or sulphur-, preferably nitrogen-, containing ring, for example pyridine.
Preferably W
1
is a straight-chain alkylene group, most preferably 1,2-ethylene.
Most preferred groups are the groups of formula (IVA), (IVB), (IVC), (IVD) and (IVE) as defined below: monomers containing such groups may be used alone or in combination with further zwitterionic monomers to provide a copolymer. Of these groups (IVB) are particularly preferred.
The groups of formula (IVA) are:
where the groups R
6
are the same or different and each is hydrogen or C
1-4
alkyl and d is from 2 to 4.
Preferably the groups R
6
are the same. It is also preferable that at least one of the groups R
6
is methyl, and more preferable that the groups R
6
are both methyl.
Preferably d is 2 or 3, more preferably 3.
When X is a group of formula (IVA) preferably B is a group of formula —(CR
3
2
)— or —(CR
3
2
)
2
—, eg. —(CH
2
)— or —(CH
2
,CH
2
)—.
The groups of formula (IVB) are:
were the groups R
7
are the same or different and each is hydrogen or C
1-4
alkyl, and e is from 1 to 4.
Preferably the groups R
7
are the same. It is also preferable that at least one of the groups R
7
is methyl, and more preferable that the groups R
7
are all methyl.
Preferably e is 2 or 3, more preferably 2.
When X is a group of formula (IVB) preferably B is a group of formula —(CR
3
2
)— or —(CR
3
2
)
2
—, eg. —(CH
2
)— or —(CH
2
CH
2
)—.
The groups of formula (IVC) are:
wherein the groups R
8
are the same or different and each is hydrogen or C
1-4
alkyl, R
8a
is hydrogen or, more preferably, a group —C(O)B
1
R
8b
where R
8b
is hydrogen or methyl, preferably methyl, B
1
is a valence bond or straight or branched alkylene, oxaalkylene or oligo-oxaalkalyene group, and f is from 1 t

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