Polymers containing zwitterionic monomers
First Claim
Patent Images
1. A cross-linkable polymer formed from monomers includinga) a hydroxyl-group containing monomer of the formula I in which R26 is hydrogen or a C1-4-alkyl group;
- A1 is —
O—
or —
NR27—
where R27 is hydrogen or a C1-4-alkyl group or a group B9R—
(OH)n;
B9 is a bond, a straight or branched alkylene, oxa alkylene or oligooxa alkylene group;
R13 is a n+1 functional C2-6 alkylene group, and n is an integer of one or more;
b) a reactive monomer of the formula (II)in which R19 is hydrogen or a C1-4-alkyl group;
A2 is —
O—
or —
NR21—
where R21 is hydrogen, or a C1-4-alkyl group R12 is a C1-24 straight or branched alkylene, oxaalkylene or oligo oxaalkylene group in which each alkylene group has 1 to 6 carbon atoms;
A3 is a bond or —
O—
; and
each R16 is independently selected from C1-6-alkyl groups; and
c) a zwitterionic monomer of the 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, a valence bond;
X is a zwitterionic group R is hydrogen or a C1-C4 alkyl group; and
A is —
O—
or —
NR1—
where R1 is hydrogen or a C1-C4 alkyl group or R1 is —
B—
X where B and X are as defined above.
2 Assignments
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Accused Products
Abstract
A cross-linkable polymer formed from monomer including
a) a hydroxyl-group containing monomer of the formula I
in which R26 is hydrogen or a C1-4-alkyl group;
A1 is —O— or —NR27— where R27 is hydrogen or a C1-4-alkyl group or a group B9R—(OH)n;
B9 is a bond, a straight or branched alkylene, oxa alkylene or oligooxa alkylene group;
R13 is a n+1 functional C1-24 alkylene group which may be substituted, and
n is an integer of one or more;
b) a reactive monomer of the formula (II)
in which R19 is hydrogen or a C1-4-alkyl group;
A2 is —O— or —NR21— where R21 is hydrogen, or a C1-4-alkyl group
R12 is a C1-24 straight or branched alkylene, oxaalkylene or oligo oxaalkylene group in which each alkylene group has 1 to 6 carbon atoms;
A3 is a bond or —O—; and
each R16 is independently selected from C1-6-alkyl groups. Preferably the polymer includes a zwitterionic monomer and is useful for providing stable biocompatible coatings on substrates.
41 Citations
29 Claims
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1. A cross-linkable polymer formed from monomers including
a) a hydroxyl-group containing monomer of the formula I in which R26 is hydrogen or a C1-4-alkyl group; -
A1 is —
O—
or —
NR27—
where R27 is hydrogen or a C1-4-alkyl group or a group B9R—
(OH)n;
B9 is a bond, a straight or branched alkylene, oxa alkylene or oligooxa alkylene group;
R13 is a n+1 functional C2-6 alkylene group, and n is an integer of one or more;
b) a reactive monomer of the formula (II) in which R19 is hydrogen or a C1-4-alkyl group;
A2 is —
O—
or —
NR21—
where R21 is hydrogen, or a C1-4-alkyl groupR12 is a C1-24 straight or branched alkylene, oxaalkylene or oligo oxaalkylene group in which each alkylene group has 1 to 6 carbon atoms;
A3 is a bond or —
O—
; and
each R16 is independently selected from C1-6-alkyl groups; and
c) a zwitterionic monomer of the 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, a valence bond;
X is a zwitterionic group R is hydrogen or a C1-C4 alkyl group; and
A is —
O—
or —
NR1—
where R1 is hydrogen or a C1-C4 alkyl group or R1 is —
B—
X where B and X are as defined above.- View Dependent Claims (2, 3, 4, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 23, 24, 25, 27, 28)
i) the group of formula (IVA) are: where the groups R6 are the same or different and each is hydrogen or a C1-4 alkyl group, and d is from 2 to 4;
ii) the group of formula (IVB) are;
where the groups R7 are the same or different and each is hydrogen or a C1-4 alkyl group, and e is from 1 to 4;
iii) the group of formula (IVC) are;
wherein the groups R8 are the same or different and each is hydrogen or a C1-4 alkyl group, R8a is hydrogen or a group —
C(O)B1R8b where R8b is hydrogen or a methyl group,B1 is a valence bond or straight or branched alkylene, oxaalkylene or oligo-oxaalkalyene group, f is from 1 to 4; and
if B is other than a valence bond, z is 1 and if B is a valence bond, z is 0, if X is directly bonded to an oxygen or nitrogen atom and otherwise z is 1;
iv) the group of formula (IVD) are;
wherein the groups R9 are the same or different and each is hydrogen or a C1-C4 alkyl group, R9a is a hydrogen or a group —
C(O)B2R9b, R9b is hydrogen or a methyl group,B2 is a valence bond or a straight or branched alkylene, oxaalkylene or oligo-oxaalkylene group;
g is from 1 to 4; and
if B is other than a valence bond, z is 1 and if B is a valence bond, z is 0 if X is directly bonded to an oxygen or nitrogen atom and otherwise z is 1;
v) the group of formula (I′
VE) are;
wherein the groups R10 are the same or different and each is hydrogen or a group —
C(O)B3R10b where R10b is hydrogen or a C1-4 alkyl group,R10a is hydrogen or a methyl group, B3 is a valence bond or a straight or branched alkylene, oxaalkylene or oligo-oxaalkylene group;
h is from 1 to 4; and
if B is other than a valence bond, z is 1 and if B is a valence bond, z is 0 if X is directly bonded to the oxygen or nitrogen and otherwise z is 1.
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4. A polymer according to claim 1 in which the monomers include a comonomer of the formula V
in which R14 is hydrogen or a C1-4-alkyl group A4 is — - O—
or —
NR15—
where R15 is hydrogen, a C1-4-alkyl group or a group Q, and Q is selected from hydroxyl groups;
a straight or branched alkyl, alkoxyalkyl or (oligo-alkoxy)alkyl chain containing 1 to 24 carbon atoms unsubstituted or substituted by one or more fluorine atoms and optionally containing one or more carbon—
carbon double or triple bonds;
a siloxane group —
(CR16b2)qq(SiR 16b2)(OSiR16b2)ppR16b in which each group R16a is the same or different and is hydrogen or an alkyl group of 1 to 4 carbon atoms or an aralkyl group, each group R16b is an alkyl group of 1 to 4 carbon atoms, qq is from 1 to 6 and pp is from 0 to 49, andC1-24-alkyl groups substituted with a group Q5 selected from anionic groups selected from carboxylate, sulphonate, hydrogenphosphate and phosphate groups and cationic groups —
+NR313 in which each group R31 is the same or different, and is hydrogen or an alkyl group of 1 to 6 carbon atoms two of which groups R31 may together form a heterocyclic ring containing from 5 to 7 atoms, —
+NHet where Het is an unsaturated heterocyclic group substituted or unsubstituted by one or more alkyl groups of 1 to 4 carbon atoms, and groups —
P+R323 in which each group R32 is the same or different and is hydrogen or an alkyl group of 1 to 6 carbons atoms, two of which groups R32 may together form a heterocyclic ring containing from 5 to 7 atoms.
- O—
-
5. A coating composition comprising a liquid vehicle and a polymer according to claim 1 dissolved or dispersed in the vehicle.
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6. A composition according to claim 5 in which the liquid vehicle includes a solvent for the polymer in which the polymer is dissolved.
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7. A crosslinked polymer formed by subjecting a polymer according to claim 1 to condition such that cross-linking takes place between the OH group of monomer I and one of the said OR16 groups of monomer II.
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9. A process of cross-linking a polymer according to claim 1 in which the polymer is subjected to conditions such that cross-linking takes place between the OH group of monomer I and one of the said OR16 groups of monomer II.
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10. A process according to claim 9 further comprising the step of coating the polymer on a substrate prior to the cross-linking reaction.
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11. A product comprising a substrate coated with a cross-linked polymer which is formed by crosslinking a polymer according to claim 1.
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12. A polymer according to claim 2 in which the zwitterionic group is an ammonium phosphate ester group.
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13. A polymer according to claim 3 in which the zwitterionic group X is of the formula IVB in which each of the groups R7 is a C1-4 alkyl group.
-
14. A polymer according to claim 13 in which each of the groups R7 is a methyl group.
-
15. A polymer according to claim 14 in which e is 2 or 3.
-
16. A polymer according to claim 14 in which the monomers include 1 to 95% by mole of a comonomer of the formula V
in which R14 is hydrogen or a C1-4-alkyl group A4 is — - O—
or —
NR15—
where R15 is selected from the group consisting of hydrogen, a C1-4-alkyl group and a group Q,and Q is selected from the group consisting of hydroxyl groups;
straight and branched alkyl, alkoxyalkyl and (oligo-alkoxy)alkyl groups containing 1 to 24 carbon atoms unsubstituted or substituted by one or more fluorine atoms and optionally containing one or more carbon—
carbon double or triple bonds;
siloxane groups —
(CR16a2)qq(SiR16b2)(OSiR16b2)ppR16b in which each group R16a is the same or different and is selected from the group consisting of hydrogen, an alkyl group of 1 to 4 carbon atoms and an aralkyl group, each group R16b is an alkyl group of 1 to 4 carbon atoms, qq is from 1 to 6 and pp is from 0 to 49; and
C1-24-alkyl groups substituted with a group Q5 selected from anionic groups selected from carboxylate, sulphonate, hydrogenphosphate and phosphate groups and cationic groups —
+NR313 in which each group R31 is the same or different, and is hydrogen or an alkyl group of 1 to 6 carbon atoms, two of which groups R31 may together form a heterocyclic ring containing from 5 to 7 atoms, —
+NHet where Het is an unsaturated heterocyclic group substituted or unsubstituted by one or more alkyl groups of 1 to 4 carbon atoms, and groups —
P+R323 in which each group R32 is the same or different and is hydrogen or an alkyl group of 1 to 6 carbons atoms, two of which groups R32 may together form a heterocyclic ring containing from 5 to 7 atoms.
- O—
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17. A polymer according to claim 4 in which Q is an alkyl group (CR172)mCR173 wherein the groups CR172 are the same or different and in each group CR172 the groups R17 are the same or different, each group R17 is selected from the group consisting of hydrogen, fluorine and a C1-4-alkyl and -fluoroalkyl group and m is 5 to 23.
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18. A polymer according to claim 17 in which each R17 is hydrogen.
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23. A coating composition comprising a liquid vehicle and a polymer according to claim 16.
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24. A cross-linked polymer formed by subjecting a polymer according to claim 16 to conditions such that cross-linking takes place between the OH group of monomer I and one of the said OR16 groups of monomer II.
-
25. A process of crosslinking a polymer according to claim 16 in which the polymer is subjected to conditions such that crosslinking takes place between the OH group derived from the monomer of the formula I and one of the said OR16 groups.
-
27. A process according to claim 25 in which the conditions include heating the polymer to a temperature of about 70°
- C.
-
28. A product comprising a substrate coated with crosslinked polymer formed by crosslinking a polymer according to claim 16.
-
8. A process of polymerising monomers, comprising the step of radical polymerisation of:
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a) a hydroxyl-group containing monomer of the formula I in which R26 is hydrogen or a C1-4 alkyl group;
A1 is —
O—
or —
NR27—
where R27 is hydrogen or a C1-4-alkyl group or a group B9R—
(OH)n;
B9 is a bond, a straight or branched alkylene, oxa alkylene or oligooxa alkylene group;
R13 is a n+1 functional C2-6 alkylene group; and
n is an integer of one or more; and
b) a reactive monomer of the formula (II) in which R19 is hydrogen or a C1-4-alkyl group or;
A2 is —
O—
or —
NR21—
where R21 is hydrogen or a C1-4-alkyl group;
R12 is C1-24 straight or branched alkylene, oxaalkylene or oligo oxaalkylene group in which each alkylene group has 1 to 6 carbon atoms;
A3 is a bond or —
O—
; and
each R16 is independently selected from C1-6-alkyl groups; and
c) a zwitterionic monomer of the 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 a valence bond;
X is a zwitterionic group R is hydrogen or a C1-C4 alkyl group; and
A is —
O—
or —
NR1—
where R1 is hydrogen or a C1-C4 alkyl group or R1 is —
B—
X where B and X are as defined above.
-
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19. A cross-linkable polymer formed from monomers including
a) a hydroxyl-group containing monomer of the general formula I in which R26 is hydrogen or a C1-4-alkyl group; -
A1 is —
O—
or —
NR27—
where R27 is selected from the group consisting of hydrogen, a C1-4-alkyl group and a group B9R—
(OH)n;
B9 is selected from the group consisting of a bond, and a straight and branched alkylene, oxa alkylene and oligooxa alkylene group;
R13 is a n+1 functional C1-24 alkylene group which may be substituted, and n is an integer of 1 or more;
b) 2 to 10% by mole of a reactive monomer of the general formula (II) in which R19 is hydrogen or a C1-4-alkyl group;
A2 is —
O—
or —
NR21—
where R21 is selected from the group consisting of hydrogen, and a C1-4-alkyl group;
R12 is selected from the group consisting of a C1-24 straight and branched alkylene, oxaalkylene and oligo oxaalkylene group in which each alkylene group or moiety has 1 to 6 carbon atoms;
A3 is a bond or —
O—
; and
each R16 is independently an C1-6-alkyl group;
c) a zwitterionic monomer of the general formula (III) wherein B is selected from the group consisting of a straight and branched alkylene, oxaalkylene and oligo-oxaalkylene group optionally containing one or more fluorine atoms up to and including perfluorinated chains and, if X contains a carbon—
carbon chain between B and the zwitterionic moiety, a valence bond;
X is a zwitterionic group R is hydrogen or a C1-C4 alkyl group; and
A is —
O—
or —
NR1—
where R1 is selected from the group consisting of hydrogen and a C1-C4 alkyl group and —
B—
X where B and X are as defined above; and
d) a comonomer of the formula V in which R14 is hydrogen or a C1-4-alkyl group A4 is —
O—
or —
NR15—
where R15 is selected from the group consisting of hydrogen, a C1-4-alkyl group and a group Q, andQ is an alkyl group (CR172)mCR173 wherein the groups CR172 are the same or different and in each group CR172 the groups R17 are the same or different, each group R17 is selected from the group consisting of hydrogen, fluorine and a C1-4-alkyl and -fluoroalkyl group and m is 5 to 23. - View Dependent Claims (20, 21, 22, 26, 29)
i) the groups of formula (IVA) are: where the groups R6 are the same or different and each is hydrogen or a C1-4 alkyl group and d is from 2 to 4;
ii) the groups of formula (IVB) are;
where the groups R7 are the same or different and each is hydrogen or a C1-4 alkyl group, and e is from 1 to 4;
iii) the groups of formula (IVC) are;
wherein the groups R8 are the same or different and each is hydrogen or a C1-4 alkyl group, R8a is hydrogen or a group —
C(O)B1R8b where R8b is hydrogen or a methyl group,B1 is selected from the group consisting of a valence bond, and a straight and branched alkylene, oxaalkylene and oligo-oxaalkylene group, f is from 1 to 4; and
if B is other than a valence bond, z is 1 and if B is a valence bond, z is 0;
iv) the groups of formula (IVD) are;
wherein the groups R9 are the same or different and each is hydrogen or a C1-C4 alkyl group, R9 is a hydrogen or a group —
C(O)B2R9b, R9b is hydrogen or a methyl group,B2 is selected from the group consisting of a valence bond and a straight and branched alkylene, oxaalkylene and oligo-oxaalkylene group;
g is from 1 to 4; and
if B is other than a valence bond, z is 1 and if B is a valence bond, z is 0;
v) the groups of formula (IVE) are;
wherein the groups R10 are the same or different and each is hydrogen or a group —
C(O)B3R10b where R10b is hydrogen or a C1-4 alkyl group,R10a is hydrogen or a methyl group, B3 is selected from a valence bond and straight and a branched alkylene, oxaalkylene and oligo-oxaalkylene group;
h is from 1 to 4; and
if B is other than a valence bond, z is 1 and if B is a valence bond, z is 0.
-
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22. A polymer according to claim 21 in which the zwitterionic group X is of the formula IVB in which each of the groups R7 is a C1-4 alkyl group.
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26. A process of crosslinking a polymer according to claim 19 in which the polymer is subjected to conditions such that crosslinking takes place between the OH group derived from the monomer of the formula I and one of the OR16 groups.
-
29. A process according to claim 26 in which conditions include heating the polymer to a temperature of about 70°
- C.
Specification
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Current AssigneeBiocompatibles Incorporated (Boston Scientific Corporation)
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Original AssigneeBiocompatibles Incorporated (Boston Scientific Corporation)
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InventorsRowan, Lee
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Primary Examiner(s)Wu, David W.
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Assistant Examiner(s)ZALUKAEVA, TATYANA
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Application NumberUS09/341,476Time in Patent Office1,639 DaysField of Search526/277, 526/278, 526/310, 526/312, 526/328, 526/328.5, 526/279, 427/372.2, 427/383.1, 427/387, 427/388.5US Class Current526/277CPC Class CodesA61F 9/00781 Apparatus for modifying int...C08F 230/085 the monomer being a polymer...
