US4826945A
Expired / Lapsed
US
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Biodegradable polymeric materials based on polyether glycols, processes for the preparation thereof and surgical articles made therefrom
Assignee: Yissum Research Development Co of Hebrew University of Jerusalem
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Filing: 1988-06-02
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Granted: 1989-05-02
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Expires: 2008-06-02
Abstract
Abstract The invention provides poly(α-hydroxy-carboxylic acid)/poly(oxyalkylene) polymers selected from multiblock polymers of the following repeating unit I ##STR1## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded, and chain extended multiblock polymers which polymers are bioabsorbable and biodegradable, these polymeric materials being derived from reacting diols in the form of polyether glycols with α-hydroxy-carboxylic acids. The invention also provides methods for the preparation of such polymeric materials and bioabsorbable surgical articles made therefrom.
Inventors
- 👤 Daniel Cohn
- 👤 Hani Younes
- 👤 Gideon Uretzky
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 15:10
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/66; A; A61; A61K; A61K47/00; A61K47/30; A61K47/34; A61L; A61L17/00; A61L17/06; A61L17/10; A61L17/12; A61L27/00; A61L27/14; A61L27/18; A61L27/50; A61L27/58; A61L31/00; A61L31/04; A61L31/06; C08G18/00; C08G18/06; C08G18/28; C08G18/40; C08G18/42; C08G18/4266; C08G18/4283; C08G2230/00; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31565; Y10T428/31786
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
170 words
A poly(α-hydroxy-carboxylic acid)/poly(oxyalkylene) polymer selected from: (a) a multiblock polymer of the following repeating unit I ##STR11## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded, or (b) a chain extended multiblock polymer of the following formula II: ##STR12## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups and R' is hexamethylene, 4,4'-diphenylmethane, toluene, naphtalene, 4,4'-dicyclohexylmethane, cyclohexyl, 3,3'-dimethylphenyl, 3,3'-dimethyl-diphenylmethane, 4,6'-xylylene, 3,5,5-trimethylcyclohexyl, 2,2,4-trimethyl-hexamethylene and p-phenylene, or diisocyanate terminated polyalkylene glycol chains comprising a central polyalkylene glycol chain capPed by two diisocyanate compounds of the above, or (c) a chain extended multiblock polymer of the following formula III ##STR13## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups, R" is a saturated or unsaturated allkylene group, or an aromatic ring, x and y are identical or different positive integers, and m is a positive integer.
Claim 2
Dependent Claim
170 words
A poly(α-hydroxy-carboxylic acid)/poly(oxyalkylene) polymer selected from: (a) a multiblock polymer of the following repeating unit I ##STR11## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded, or (b) a chain extended multiblock polymer of the following formula II: ##STR12## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups and R' is hexamethylene, 4,4'-diphenylmethane, toluene, naphtalene, 4,4'-dicyclohexylmethane, cyclohexyl, 3,3'-dimethylphenyl, 3,3'-dimethyl-diphenylmethane, 4,6'-xylylene, 3,5,5-trimethylcyclohexyl, 2,2,4-trimethyl-hexamethylene and p-phenylene, or diisocyanate terminated polyalkylene glycol chains comprising a central polyalkylene glycol chain capPed by two diisocyanate compounds of the above, or (c) a chain extended multiblock polymer of the following formula III ##STR13## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups, R" is a saturated or unsaturated allkylene group, or an aromatic ring, x and y are identical or different positive integers, and m is a positive integer.
Claim 3
Dependent Claim
56 words
A multiblock copolymer useful for the manufacture of bioabsorbable surgical articles, having a general repeating unit I ##STR14## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded.
Claim 4
Dependent Claim
56 words
A multiblock copolymer useful for the manufacture of bioabsorbable surgical articles, having a general repeating unit I ##STR14## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded.
Claim 5
Dependent Claim
12 words
A multiblock copolymer as claimed in claim 1 where R is ethylene.
Claim 6
Dependent Claim
13 words
A multiblock copolymer as claimed in claim 1 where R 1 is hydrogen.
Claim 7
Dependent Claim
13 words
A multiblock copolymer as claimed in claim 1 where R 1 is methyl.
Claim 8
Dependent Claim
24 words
A multiblock copolymer as claimed in claim 1 wherein along the copolymeric chain some R 1 s are hydrogen and some are methyl groups.
Claim 9
Dependent Claim
72 words
A multiblock copolymer having the following general formula: ##STR15## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups and R' is hexamethylene, 4,4'-diphenylmethane, toluene, naphtalene, 4,4'-dicyclohexylmethane, cyclohexyl, 3,3'-dimethylphenyl, 3,3'-dimethyl-diphenylmethane, 4,6'-xylylene, 3,5,5-trimethylcyclohexyl, 2,2,4-trimethyl-hexamethylene and p-phenylene, or diisocyanate-terminated polyalkylene glycol chains comprising a central polyalkylene glycol chain capped by two diisocyanate compounds of the above, x and y are identical or different positive integers and m is a positive integer.
Claim 10
Dependent Claim
72 words
A multiblock copolymer having the following general formula: ##STR15## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups and R' is hexamethylene, 4,4'-diphenylmethane, toluene, naphtalene, 4,4'-dicyclohexylmethane, cyclohexyl, 3,3'-dimethylphenyl, 3,3'-dimethyl-diphenylmethane, 4,6'-xylylene, 3,5,5-trimethylcyclohexyl, 2,2,4-trimethyl-hexamethylene and p-phenylene, or diisocyanate-terminated polyalkylene glycol chains comprising a central polyalkylene glycol chain capped by two diisocyanate compounds of the above, x and y are identical or different positive integers and m is a positive integer.
Claim 11
Dependent Claim
37 words
A multiblock copolymer as claimed in claim 7, where R is ethylene and the diisocyanate is hexamethylene diisocyanate (HDI), the polymer being of the formula ##STR16## wherein R 1 , x, y and m are as defined.
Claim 12
Dependent Claim
22 words
A multiblock copolymer as claimed in claim 7, where the dissocyanate is 4,4'-diphenylmethane diisocyanate (MDI), the polymer being of the formula ##STR17##
Claim 13
Dependent Claim
19 words
A multiblock copolymer according to claim 1, wherein said copolymer is in the form of at least one filament.
Claim 14
Dependent Claim
50 words
A surgical article selected from the group consisting of a suture, ligature, needle and suture combination, surgical clip, surgical staple, surgical prosthesis, textile structure, coupling, tube, support, screw or pin, where at least one of the components of each of said articles is a polymer as claimed in claim 1.
Claim 15
Dependent Claim
41 words
A compound vascular prosthesis in which a non-biodegradable graft is coated with a polymer or polymers as claimed in claim 1, the prosthesis being blood tight at implantation, and becoming, in time, sufficiently porous to facilitate tissue ingrowth and biological healing.
Claim 16
Dependent Claim
25 words
A compound vascular prosthesis as claimed in claim 12, where a knitted Dacron graft is coated with a multiblock copolymer as claimed in claim 1.
Claim 17
Dependent Claim
15 words
A substantially biodegradable vascular prosthesis comprising non-absorbable polymers and polymers as claimed in claim 1.
Claim 18
Dependent Claim
37 words
A substantially biodegradable vascular prosthesis comprising a non absorbable component selected from polyethylene terephthalate and/or polyether urethanes and/or polyether esters and/or polydimethyl siloxane polymers or copolymers, and polymers as claimed in claim 1 as the absorbable component.
Claim 19
Dependent Claim
18 words
A totally biodegradable vascular prosthesis manufactured by textile and non-textile techniques, comprising polymers as claimed in claim 1.
Claim 20
Dependent Claim
18 words
A partially biodegradable wound or burn covering comprising non absorbable polymers and polymers as claimed in claim 1.
Claim 21
Dependent Claim
13 words
A biodegradable wound or burn dressing, comprising polymers as claimed in claim 1.
Claim 22
Dependent Claim
129 words
A process of producing a multiblock copolymer having a general repeating unit I ##STR18## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded, produced by adding monomeric α-hydroxy carboxylic acids of the formula ##STR19## to hydroxyl-ended poly(alkylene glycol) chains, the polycondensation reaction taking place in the presence of an esterification promoting catalyst at a temperature of about 120° to 160° C., subsequently raising the temperature to about 200° C. for about 16 hours, with constant flow of dry nitrogen and then lowering the temperature to about 135° C. while a 5 mm Hg vacuum is applied for about 4 hours.
Claim 23
Dependent Claim
129 words
A process of producing a multiblock copolymer having a general repeating unit I ##STR18## wherein R is an alkylene group, R 1 is hydrogen or methyl groups, m is a positive integer, and a and b are zero or positive integers, the case where a and b are simultaneously zero being excluded, produced by adding monomeric α-hydroxy carboxylic acids of the formula ##STR19## to hydroxyl-ended poly(alkylene glycol) chains, the polycondensation reaction taking place in the presence of an esterification promoting catalyst at a temperature of about 120° to 160° C., subsequently raising the temperature to about 200° C. for about 16 hours, with constant flow of dry nitrogen and then lowering the temperature to about 135° C. while a 5 mm Hg vacuum is applied for about 4 hours.
Claim 24
Dependent Claim
15 words
A process according to claim 19 wherein said catalyst is Sb 2 O 3 .
Claim 25
Dependent Claim
115 words
A process for chain extending triblock copolymers of formula IV ##STR20## wherein R, X, y and m are as defined, said triblock polymers, which are produced by the polycondensation reaction of monomeric α-hydroxy carboxylic acid, having the formula ##STR21## in the presence of hydroxyl-terminated poly(alkylene glycol) chains, are extended by adding to the polymers produced thereby, a diisocyanate chain extension agent of general formula OCN--R'--NCO, wherein R' is hexamethylene, 4,4'-diphenylmethane, toluene, naphtalene, 4,4'-dicyclohexylmethane, cyclohexyl, 3,3'-dimethylphenyl, 3,3'-dimethyl-diphenylmethane, 4,6'-xylylene, 3,5,5-trimethylcyclohexyl, 2,2,4-trimethyl-hexamethylene and p-phenylene, or diisocyanate-terminated polyalkylene glycol chains comprising a central polyalkylene glycol chain capped by two diisocyanate compounds of the above, x and y are identical or different positive integers and m is a positive integer.
Claim 26
Dependent Claim
115 words
A process for chain extending triblock copolymers of formula IV ##STR20## wherein R, X, y and m are as defined, said triblock polymers, which are produced by the polycondensation reaction of monomeric α-hydroxy carboxylic acid, having the formula ##STR21## in the presence of hydroxyl-terminated poly(alkylene glycol) chains, are extended by adding to the polymers produced thereby, a diisocyanate chain extension agent of general formula OCN--R'--NCO, wherein R' is hexamethylene, 4,4'-diphenylmethane, toluene, naphtalene, 4,4'-dicyclohexylmethane, cyclohexyl, 3,3'-dimethylphenyl, 3,3'-dimethyl-diphenylmethane, 4,6'-xylylene, 3,5,5-trimethylcyclohexyl, 2,2,4-trimethyl-hexamethylene and p-phenylene, or diisocyanate-terminated polyalkylene glycol chains comprising a central polyalkylene glycol chain capped by two diisocyanate compounds of the above, x and y are identical or different positive integers and m is a positive integer.
Claim 27
Dependent Claim
19 words
A process as claimed in claim 21, where R is ethylene, R 1 is methyl and R" is hexamethylene.
Claim 28
Dependent Claim
50 words
A multiblock copolymer having the following general formula III ##STR22## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups, R" is an alkylene saturated or unsaturated group or an aromatic ring, x and y are identical or different positive integers, and m is a positive integer.
Claim 29
Dependent Claim
50 words
A multiblock copolymer having the following general formula III ##STR22## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups, R" is an alkylene saturated or unsaturated group or an aromatic ring, x and y are identical or different positive integers, and m is a positive integer.
Claim 30
Dependent Claim
20 words
A multiblock copolymer as claimed in claim 23, where R is ethylene, R 1 is methyl and R" is ethylene.
Claim 31
Dependent Claim
15 words
A multiblock copolymer as claimed in claim 24, where R" is an unsaturated CH═CH group.
Claim 32
Dependent Claim
75 words
A process for chain extending the triblock copolymers presented in claim 23, by adding to them carboxylic acids and derivatives as chain extention agents, the multiblock copolymers produced thereby having the following formula III ##STR23## wherein R represents an alkylene group, R 1 is hydrogen or methyl groups, R" is an alkylene saturated or unsaturated group or an aromatic ring, x and y are identical or different positive integers, and m is a positive integer.
Claim 33
Dependent Claim
50 words
A surgical article selected from the group consisting of a suture, ligature, needle and suture combination, surgical clip, surgical staple, surgical prosthesis, textile structure, coupling, tube, support, screw or pin, where at least one of the components of each of said articles is a polymer as claimed in claim 7.
Claim 34
Dependent Claim
41 words
A compound vascular prosthesis in which a non-biodegradable graft is coated with a polymer or polymers as claimed in claim 7, the prosthesis being blood tight at implantation, and becoming, in time, sufficiently porous to facilitate tissue ingrowth and biological healing.
Claim 35
Dependent Claim
25 words
A compound vascular prosthesis as claimed in claim 28, where a knitted Dacron graft is coated with a multiblock copolymer as claimed in claim 7.
Claim 36
Dependent Claim
15 words
A substantially biodegradable vascular prosthesis comprising non-absorbable polymers and polymers as claimed in claim 7.
Claim 37
Dependent Claim
36 words
A substantially biodegradable vascular prosthesis comprising a non-absorbable component selected from polyethylene terephthalate and/or polyether urethanes and/or polyether esters and/or polydimethyl siloxane polymers or copolymers, and polymers as claimed in claim 7 as the absorbable components.
Claim 38
Dependent Claim
18 words
A totally biodegradable vascular prosthesis manufactured by textile and non-textile techniques, comprising polymers as claimed in claim 7.
Claim 39
Dependent Claim
50 words
A surgical article selected from the group consisting of a suture, ligature, needle and suture combination surgical clip, surgical staple, surgical prosthesis, textile structure, coupling, tube support, screw or pin, where at least one of the components of each of said articles is a polymer as claimed in claim 23.
Claim 40
Dependent Claim
41 words
A compound vascular prosthesis in which a non-biodegradable graft is coated with a polymer or polymers as claimed in claim 23, the prosthesis being blood tight at implantation, and becoming, in time, sufficiently porous to facilitate tissue ingrowth and biological healing.
Claim 41
Dependent Claim
25 words
A compund vascular prosthesis as claimed in claim 34, where a knitted Dacron graft is coated with a multiblock copolymer as claimed in claim 23.
Claim 42
Dependent Claim
15 words
A substantially biodegradable vascular prosthesis comprising non-absorbable polymers and polymers as claimed in claim 23.
Claim 43
Dependent Claim
36 words
A substantially biodegradable vascular prosthesis comprising a non-absorbable component selected from polyethylene terephthalate and/or polyether urethanes and/or polyether esters and/or Polydimethyl siloxane polymers or copolymers, and polymers as claimed in claim 23 as the absorbable components.
Claim 44
Dependent Claim
19 words
A totally biodegradable vascular prosthesis manufactured by textile and non textile techniques, comprising polymers as claimed in claim 23.
Claim 45
Dependent Claim
17 words
A partially biodegradable wound or burn covering comprising non-absorbable polymers and polymers as claimed in claim 7.
Claim 46
Dependent Claim
13 words
A biodegradable wound or burn dressing comprising polymers as claimed in claim 7.
Claim 47
Dependent Claim
17 words
A partially biodegradable wound or burn dressing comprising non-absorbable polymers and polymers as claimed in claim 23.
Claim 48
Dependent Claim
13 words
A biodegradable wound or burn dressing comprising polymers as claimed in claim 23.
Claim 49
Dependent Claim
30 words
A pharmaceutical composition comprising a self-supporting film, hollow tube, beads or gel, manufactured from a multiblock copolymer as claimed in claim 1 and containing a uniformly dispersed drug contained therein.
References Cited (Backward Citations)
US4355133A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-05-01 | 1992-10-31 | 1993-05-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-05-01 | 1996-10-31 | 1997-05-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-05-01 | 2000-10-31 | 2001-05-02 | $7700.00 | Window Closed / Lapsed |