Hydrogels of absorbable polyoxaesters containing amines or amido groups
First Claim
1. A crosslinked aliphatic polyoxaester comprising a polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked.
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Accused Products
Abstract
The present invention describes a crosslinked aliphatic polyoxaesters containing amines and/or amido groups and blends thereof with other polymers that may be used to produce surgical devices such as sutures, sutures with attached needles, molded devices, and the like. The crosslinked aliphatic polyoxaesters of the present invention is formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I:
O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--
!I
and a second repeating unit of the formula:
--O--R.sub.12 --!.sub.U, XVI
and optionally a third repeating unit with a formula selected from the group consisting of:
--O--R.sub.4 --!.sub.A, II
--O--R.sub.5 --C(O)--!.sub.B, III
( --O--R.sub.5 --C(O)!.sub.P --O--).sub.L G XI
and combinations thereof wherein R12 contains an internal amine or internal amide group wherein the aliphatic polyoxaester has been crosslinked.
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Citations
67 Claims
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1. A crosslinked aliphatic polyoxaester comprising a polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked. - View Dependent Claims (2, 3, 4, 5)
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6. A device made from a crosslinked aliphatic polyoxaester comprising an aliphatic polyoxaester, a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked. - View Dependent Claims (7, 8, 9, 10, 11, 12, 13, 14)
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15. A coated device comprising an aliphatic polyoxaesters having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit of formula;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVand combinations thereof, wherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked. - View Dependent Claims (16, 17, 18, 19, 20, 21)
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22. A drug delivery matrix comprising a drug and a crosslinked aliphatic polyoxaester wherein the crosslinked aliphatic polyoxaester is formed from an aliphatic polyoxaester has a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit of formula;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000. - View Dependent Claims (23, 24, 25)
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26. A crosslinked aliphatic polyoxaester comprising an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating unit of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, and III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--,--CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the aliphatic polyoxaester has been crosslinked. - View Dependent Claims (27, 29)
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28. A device made from a crosslinked aliphatic polyoxaesters comprising an aliphatic polyoxaester that has a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C. is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the aliphatic polyoxaester has been crosslinked.
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30. A coated device comprising a device coated with a crosslinked aliphatic polyoxaester is formed from an aliphatic polyoxaesters having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating unit of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the polyoxaester has been crosslinked. - View Dependent Claims (31, 62)
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32. A drug delivery matrix comprising a drug and a crosslinked aliphatic polyoxaester wherein the crosslinked aliphatic polyoxaester is formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> --O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--! Iand two second repeating unit of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the polyoxaester has been crosslinked before or after the addition of the drug. - View Dependent Claims (33)
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34. A polymer blend comprising a crosslinked aliphatic polyoxaesters formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> --O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--! Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000; and
which has been crosslinked,a second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof. - View Dependent Claims (35, 36, 37, 38)
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39. A device made from a polymer blend comprising a crosslinked aliphatic polyoxaesters formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> --O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--! Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked anda second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof. - View Dependent Claims (40, 41, 42, 43, 44, 45, 46, 47)
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48. A coated device comprising a device coated with a polymer blend of a crosslinked aliphatic polyoxaesters composed of an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit of formula;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVand combinations thereof, wherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked; anda second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof. - View Dependent Claims (49, 50, 51, 52, 53, 54)
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55. A drug delivery matrix comprising a drug and a polymer blend composed of a crosslinked aliphatic polyoxaester having a first divalent repeating unit of formula I formed from an aliphatic polyoxaester:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit of formula;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester has been crosslinked; anda second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof. - View Dependent Claims (56, 57, 58)
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59. A polymer blend comprising a crosslinked aliphatic polyoxaesters formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating units of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, and III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the aliphatic polyoxaester has been crosslinked; anda second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof. - View Dependent Claims (60)
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61. A coated device comprising a device coated with a crosslinked aliphatic polyoxaester formed from an aliphatic polyoxaesters having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating unit of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the aliphatic polyoxaester is crosslinked anda second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof.
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63. A drug delivery matrix comprising a drug and a polymer blend composed of a crosslinked aliphatic polyoxaester formed from an aliphatic polyoxaesters having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating unit of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, III
space="preserve" listing-type="equation">( --O--R.sub.13 --C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the aliphatic polyoxaester is crosslinked; anda second polymer selected from the group consisting of homopolymer and copolymer of lactone type polymers with the repeating units described by formulas III and XI, aliphatic polyurethanes, polyether polyurethanes, polyester polyurethanes, polyethylene copolymers, polyamides, polyvinyl alcohols, poly(ethylene oxide), polypropylene oxide, polyethylene glycol, polypropylene glycol, polytetramethylene oxide, polyvinyl pyrrolidone, polyacrylamide, poly(hydroxy ethyl acrylate), poly(hydroxyethyl methacrylate), absorbable polyoxalates, absorbable polyanhydrides and combinations thereof. - View Dependent Claims (64)
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65. A prepolymer comprising an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000;
wherein the aliphatic polyoxaester is chemically linked to a polymerizable region.
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66. A hydrogel comprising water and a crosslinked aliphatic polyoxaesters formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand two second repeating unit of the formulas;
space="preserve" listing-type="equation"> --O--R.sub.5 --C(O)--!.sub.B, and III
space="preserve" listing-type="equation">( --O--R.sub.13 13 C(O)!.sub.P --O--).sub.L G XIwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero, in which case E will be from 2 to 12;
R5 and R13 are different and are selected from the group consisting of --C(R6)(R7)--, --(CH2)3 --O--, --CH2 --CH2 --O--CH2 --, --CR8 H--CH2 --, --(CH2)5 --, --(CH2)F --O--C(O)-- and --(CH2)K --C(O)--CH2 --;
R6 and R7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms;
R8 is hydrogen or methyl;
F and K are integers in the range of from 2 to 6;
B is an integer in the range of from 1 to n such that the number average molecular weight of formula III is less than about 200,000;
P is an integer in the range of from 1 to m such that the number average molecular weight of formula XI is less than about 1,000,000;
G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 1 to about 200 hydroxyl groups; and
L is an integer from about 1 to about 200;
wherein the polyoxaester has been crosslinked.
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67. A hydrogel comprising water and a crosslinked aliphatic polyoxaester formed from a polyoxaester having a first divalent repeating unit of formula I:
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space="preserve" listing-type="equation"> O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--!Iand a second repeating unit selected from the group of formulas consisting of;
space="preserve" listing-type="equation"> --O--R.sub.12 --!.sub.U, XIVwherein R1 and R2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms;
R3 is an alkylene unit or is an oxyalkylene group of the following formula;
space="preserve" listing-type="equation">-- (CH.sub.2).sub.C --O--!.sub.D --(CH.sub.2).sub.E -- IVwherein C is an integer in the range of from 2 to about 5, D is an integer in the range of from about 0 to about 2,000, and E is an integer in the range of from about 2 to about 5, except when D is zero in which case E will be an integer from 2 to 12;
R12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R10)--) or amide (--N(R11)--);
R10 and R11 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; and
U is an integer in the range of from 1 to about 2,000.
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Specification