Silyl ether-modified hydrophilic polymers and uses for medical articles
View Patent ↗Silane-functionalized hydrophilic polymers and polymeric matrices are described. Hydrophilic matrices can be formed from the polymers, and can be used in association with the preparation of implantable and injectable medical devices. Exemplary devices include those having a durable lubricious coating formed from the hydrophilic polymers.
1. An implantable or insertable medical device comprising a polymeric matrix, the polymeric matrix comprising a hydrophilic polymer having pendent groups comprising a reacted silyl ether group, the matrix formed from an aqueous composition comprising hydrophilic polymer having the formula:
where R 1 comprises an organic side chain group selected from
R 2 comprises an amine group;
R 2S comprises a silyl ether group;
R 10 is independently hydrogen, methyl, or ethyl; and
wherein x, y, and z independently represent the amount of each monomer species present in the polymer in random, block, or alternating configuration, with x in the range of 85 mole % to 99 mole %, y in the range of 0 mole % to 14 mole %, and z in the range of 1 mole % to 15 mole %; and wherein
the hydrophilic polymer is present at a concentration in the range of 0.1 mg/mL to 50 mg/mL in the aqueous composition.
2. The device of claim 1 where the reacted silyl ether group has the following formula:
where M represents an atom of material of the device the polymeric matrix is in contact with, or an atom of another polymer in the matrix; X represents an atom in the polymer backbone of the hydrophilic polymer; side chain divalent segment, having one or more of C, H, O, or N”, and substitute therefor “L is selected from —NH—C(O)—NH— or —NH—C(O)—O—; R 3 is —(CO)NH(CH 2 ) m —, and m is an integer in the range of 1-6; R 4 is —(CH 2 ) n —, and n is an integer in the range of 1-6”; R 5 and R 7 are independently selected from R 8 and OR 8 , wherein R 8 is a C1-C6-containing monovalent alkyl group.
3. The device of claim 2 wherein n is 3 or 4.
4. The device of claim 2 wherein m is 3 or 4.
5. The device of claim 1 where R 2S is
wherein
R 3 is —(CO)NH(CH 2 ) m —, and m is an integer in the range of 1-6;
L is selected from —NH—C(O)—NH— and —NH—C(O)—O—;
R 4 is —(CH 2 ) n —, and n is an integer in the range of 1-6;
R 5 , R 6 , and R 7 are independently selected from R 8 and OR 8 , wherein R 8 is a linear or branched C1-C6 monovalent alkyl group, with the proviso that at least one of R 5 , R 6 , or R 7 is OR 8 .
6. The device of claim 1 which is a catheter.
7. The device of claim 1 wherein the polymeric matrix is present on an inner surface of the device.
8. A method for providing a coating to an implantable or insertable medical device comprising steps of
applying an aqueous composition to a surface of the device, the aqueous composition comprising a hydrophilic polymer comprising a pendent group comprising a reactive silyl ether group, the hydrophilic polymer having the formula:
where R 1 comprises an organic side chain group selected from
R 2 comprises an amine group;
R 2S comprises a silyl ether group;
R 10 is independently hydrogen, methyl, or ethyl; and
wherein x, y, and z independently represent the amount of each monomer species present in the polymer in random, block, or alternating configuration, with x in the range of 85 mole % to 99 mole %, y in the range of 0 mole % to 14 mole %, and z in the range of 1 mole % to 15 mole %; and present at a concentration in the range of 0.1 mg/mL to 50 mg/mL in the aqueous composition; and
heating the hydrophilic polymer to cause reaction of the silyl ether group and covalent bonding of the polymer to the surface or the device or to another hydrophilic polymer.
9. The method of claim 8 wherein the composition is an aqueous composition optionally including an alcohol.
10. The method of claim 8 wherein the method comprises a step of drying the composition on the device surface to remove liquid.
11. The method of claim 8 wherein the step of heating is performed at 100° C. or greater.
12. The device of claim 1 wherein the aqueous composition comprises a mixture of (a) water and (b) an alcohol or tetrahydrofuran.
13. An implantable or insertable medical device comprising a polymeric matrix, the polymeric matrix comprising a hydrophilic polymer having pendent groups comprising a reacted silyl ether group, wherein the polymeric matrix is formed by a polymer having the formula:
where
R 1 comprises an organic side chain group selected from
R 2 comprises an amine group;
R 2S comprises a silyl ether group;
R 10 is independently hydrogen, methyl, or ethyl; and
wherein x, y, and z independently represent the amount of each monomer species present in the polymer in random, block, or alternating configuration, with x in the range of 85 mole % to 99 mole %, y in the range of 0 mole % to 14 mole %, and z in the range of 1 mole % to 15 mole %.
14. The device of claim 13 which is a catheter, and the polymeric matrix comprises a coating on a surface of the catheter.
15. The device of claim 13 wherein the polymeric matrix is present on an inner surface of the device.
16. An implantable or insertable medical device comprising a polymeric matrix, the polymeric matrix comprising a hydrophilic polymer having pendent groups comprising a reacted silyl ether group, wherein the polymeric matrix is formed by a polymer having the formula:
where
R 1 comprises an organic side chain group;
R 2 comprises an amine group;
R 2S is
wherein
R 3 is —(CO)NH(CH 2 ) m —, and m is an integer in the range of 1-6;
L is selected from —NH—C(O)—NH— and —NH—C(O)—O—;
R 4 is —(CH 2 ) n —, and n is an integer in the range of 1-6;
R 5 , R 6 , and R 7 are independently selected from R 8 and OR 8 , wherein R 8 is a linear or branched C1-C6 monovalent alkyl group, with the proviso that at least one of R 5 , R 6 , or R 7 is OR 8 ;
R 10 is independently hydrogen, methyl, or ethyl; and
wherein x, y, and z independently represent the amount of each monomer species present in the polymer in random, block, or alternating configuration, with x in the range of 85 mole % to 99 mole %, y in the range of 0 mole % to 14 mole %, and z in the range of 1 mole % to 15 mole %.
17. The device of claim 16 which is a catheter, and the polymeric matrix comprises a coating on a surface of the catheter.
18. The device of claim 16 wherein the polymeric matrix is present on an inner surface of the device.