Absorbable polyoxaesters containing amines and/or amido groups

Claim 2

An aliphatic polyoxaesters comprising 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 selected from the group of formulas consisting of: [--O--R.sub.12 --].sub.U, XIV wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: --[(CH.sub.2).sub.C --O--].sub.D --(CH.sub.2).sub.E -- IV wherein 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 12, 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; R 12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R 10 )--) or amide (--N(R 11 )--); R 10 and R 11 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 1,000.

Claim 3

The aliphatic polyoxaester of claim 1 wherein the aliphatic polyoxaester additionally contains a third repeating unit 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.13 --C(O)].sub.P --O--).sub.L G and XI and combinations thereof; wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000; R 5 and R 13 are independently selected from the group consisting of --C(O)(R 7 )--, --(CH 2 ) 3 --O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; R 8 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12.

Claim 4

The aliphatic polyoxaesters of claim 1 wherein the polymer has the formula: [--O--C(O)--C(R.sub.1) (R.sub.2)--O--(R.sub.3)--O--C(R.sub.1) (R.sub.2)C(O)--(O--R.sub.12).sub.U --].sub.N wherein N is an integer in the range of from about 1 to about 300,000.

Claim 5

The aliphatic polyoxaesters of claim 2 wherein the polymer has the formula: [(--C(O)--C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S (C(O)--R.sub.5 --O).sub.B ].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 6

The aliphatic polyoxaesters of claim 2 wherein the polymer has the formula: [(--C(O)--C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S ([--O--R.sub.13 --C(O)].sub.P --O--).sub.L G].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 9

The device of claim 6 wherein the aliphatic polyoxaester additionally contains a third repeating unit 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.13 --C(O)].sub.P --O--).sub.L G and XI combinations thereof; wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000; R 5 and R 13 are independently selected from the group consisting of --C(O)(R 6 )(R 7 )--, --(CH 2 ) 3 --O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; R 8 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12.

Claim 10

The device of claim 6 wherein the device is an absorbable surgical device.

Claim 11

The absorbable surgical device of claim 6 wherein the absorbable surgical device is selected from the group consisting of burn dressings, hernia patches, medicated dressings, fascial substitutes, gauze, fabrics, sheets, felts, sponges, gauze bandages, arterial graft, bandages for skin surfaces, suture knot clip, pins, clamps, screws, plates, clips, staples, hooks, buttons, snaps, bone substitutes, intrauterine devices, tubes, surgical instruments, vascular implants, vascular supports, vertebral discs, and artificial skin.

Claim 12

The absorbable surgical device of claim 6 wherein the device is a filament.

Claim 13

The filament of claim 10 wherein the filament is attached to a needle.

Claim 14

The device of claim 6 wherein the aliphatic polyoxaesters have the formula: [--O--C(O)--C(R.sub.1) (R.sub.2)--O--(R.sub.3)--O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --].sub.N wherein N is an integer in the range of from about 1 to about 300,000.

Claim 15

The device of claim 6 wherein the aliphatic polyoxaesters have the formula: [(--C(O)--C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S (C(O)--R.sub.5 --O).sub.B ].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 16

The device of claim 6 wherein the aliphatic polyoxaesters have [(--C(O)--C(R.sub.1) (R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S ([--O--R.sub.13 --C(O).sub.P ]--O--).sub.L G].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 19

The device coated with an absorbable coating of claim 15 wherein the aliphatic polyoxaester additionally contains a third repeating unit 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.13 --C(O)].sub.P --O--).sub.L G and XI combinations thereof wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000; R 5 and R 13 are independently selected from the group consisting of --C(R 6 )(R 7 )--, --(CH 2 ) 3 --O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; R 8 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12.

Claim 20

The device coated with an absorbable coating of claim 15 wherein the device is a suture.

Claim 21

The device coated with an absorbable coating of claim 17 wherein the suture is attached to a needle.

Claim 22

The device coated with an absorbable coating of claim 15 wherein the aliphatic polyoxaesters have the formula: [--O--C(O)--C(R.sub.1) (R.sub.2)--O--(R.sub.3)--O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --].sub.N wherein N is an integer in the range of from about 1 to about 300,000.

Claim 23

The device coated with an absorbable coating of claim 15 wherein the aliphatic polyoxaesters have the formula: [(--C(O)--C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S (C(O)--R.sub.5 --O).sub.B ].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 24

The device coated with an absorbable coating of claim 15 wherein the aliphatic polyoxaesters have the formula: [(--C(O) --C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1)(R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S ([--O--R.sub.13 --C(O).sub.P ]--O--) .sub.L G].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 25

A drug delivery matrix comprising a drug and 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 formula: [--O--R.sub.12 ].sub.U, XIV wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: --[(CH.sub.2).sub.C --O--].sub.D --(CH.sub.2).sub.E IV wherein 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 12, 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; R 12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R 10 )--) or amide (--N(R 11 )--); R 10 and R 11 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 1,000.

Claim 26

A drug delivery matrix comprising a drug and 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 formula: [--O--R.sub.12 ].sub.U, XIV wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: --[(CH.sub.2).sub.C --O--].sub.D --(CH.sub.2).sub.E IV wherein 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 12, 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; R 12 is an alkylene unit containing from 2 to 8 carbon atoms and containing an internal amine (--N(R 10 )--) or amide (--N(R 11 )--); R 10 and R 11 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 1,000.

Claim 27

The drug delivery matrix of claim 22 wherein the aliphatic polyoxaester additionally contains a third repeating unit 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.13 --C(O)].sub.9 --O--).sub.L G and XI combinations thereof; wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000; R 5 and R 13 are independently selected from the group consisting of --C(O)(R 6 )--, --(CH 2 ) 3 --O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; R 8 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 l to n such that the number average molecular weight of formula III is less than about 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12.

Claim 28

The drug delivery matrix of claim 22 wherein the aliphatic polyoxaester has the formula: [(--C(O)--C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S (C(O)--R.sub.5 --O).sub.B ].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 29

The drug delivery matrix of claim 22 wherein the aliphatic polyoxaester has the formula: [(--C(O)--C(R.sub.1) (R.sub.2)--O--R.sub.3 --O--C(R.sub.1) (R.sub.2)--C(O)--(O--R.sub.12).sub.U --O).sub.S ([--O--R.sub.31--C(O)].sub.P --O--).sub.L G ].sub.W wherein S and W are independently integers in the range of from about 1 to about 1,000.

Claim 30

An aliphatic polyoxaesters comprising 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 two second repeating unit of the formulas: [--O--R.sub.5 --C(O)--].sub.B, and III ( [--O--R.sub.13 --C(O)].sub.P --O--).sub.L G XI wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: --[(CH.sub.2).sub.C --O--].sub.D --(CH.sub.2).sub.E -- IV wherein 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 12, 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; R 5 and R 13 are different and are selected from the group consisting of --C(O)(R 6 )(R 7 )--, --(CH 2 )3--O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; Rs 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12.

Claim 31

An aliphatic polyoxaesters comprising 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 two second repeating unit of the formulas: [--O--R.sub.5 --C(O)--].sub.B, and III ( [--O--R.sub.13 --C(O)].sub.P --O--).sub.L G XI wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: --[(CH.sub.2).sub.C --O--].sub.D --(CH.sub.2).sub.E -- IV wherein 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 12, 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; R 5 and R 13 are different and are selected from the group consisting of --C(O)(R 6 )(R 7 )--, --(CH 2 )3--O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; Rs 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12.

Claim 32

The aliphatic polyoxaester of claim 26 where additionally present is a third repeating unit of the formula: [--O--R.sub.4 --].sub.A, II wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000.

Claim 35

The aliphatic polyoxaester of claim 26 where additionally present is a third repeating unit of the formula: [--O--R.sub.4 --].sub.A, II wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000.

Claim 38

The aliphatic polyoxaester of claim 30 where additionally present is a third repeating unit of the formula: [--O--R.sub.4 --].sub.A, II wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000.

Claim 39

A drug delivery matrix comprising a drug and an aliphatic polyoxaesters 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 two second repeating unit of the formulas: [--O--R.sub.5 --C(O)--].sub.B, III ([--O--R.sub.13 --C(O)].sub.P --O--).sub.L G XI wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: [(CH.sub.2) .sub.C --O--].sub.D --(CH.sub.2).sub.E -- IV wherein 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 12, 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; R 5 and R 13 are different and are selected from the group consisting of --C(R 6 ) (R 7 )--, --(CH 2 ) 3 --O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; R 8 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12 wherein the inherent viscosity of the polyoxaester is in the range of from about 0.05 to about 2.0 deciliters per gram (dl/g) as measured in a 0.1 g/dl solution of hexafluoroisopropanol (HFIP) at 25° C.

Claim 40

A drug delivery matrix comprising a drug and an aliphatic polyoxaesters 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 two second repeating unit of the formulas: [--O--R.sub.5 --C(O)--].sub.B, III ([--O--R.sub.13 --C(O)].sub.P --O--).sub.L G XI wherein R 1 and R 2 are independently hydrogen or an alkyl group containing 1 to 8 carbon atoms; R 3 is an alkylene unit or is an oxyalkylene group of the following formula: [(CH.sub.2) .sub.C --O--].sub.D --(CH.sub.2).sub.E -- IV wherein 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 12, 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; R 5 and R 13 are different and are selected from the group consisting of --C(R 6 ) (R 7 )--, --(CH 2 ) 3 --O--, --CH 2 --CH 2 --O--CH 2 --, --CR 8 H--CH 2 --, --(CH 2 ) 4 --, --(CH 2 ) F --O--C(O)-- and --(CH 2 ) K --C(O)--CH 2 --; R 6 and R 7 are independently hydrogen or an alkyl containing from 1 to 8 carbon atoms; R 8 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 40,000; 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 40,000; G represents the residue minus from 1 to L hydrogen atoms from the hydroxyl groups of an alcohol previously containing from 2 to 12 hydroxyl groups; and L is an integer from about 1 to about 12 wherein the inherent viscosity of the polyoxaester is in the range of from about 0.05 to about 2.0 deciliters per gram (dl/g) as measured in a 0.1 g/dl solution of hexafluoroisopropanol (HFIP) at 25° C.

Claim 41

The drug delivery matrix of claim 32 wherein the aliphatic polyoxaester has additionally present a third repeating unit of the formula: [--O--R.sub.4 --].sub.A, II wherein R 4 is an alkylene unit containing from 2 to 8 carbon atoms; A is an integer in the range of from 1 to 1,000.