US4829099A
Expired / Lapsed
US
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Metabolically acceptable polyisocyanate adhesives
Assignee: Bioresearch Inc
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Filing: 1987-07-17
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Granted: 1989-05-09
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Expires: 2007-07-17
Abstract
Abstract Metabolically-acceptable, surgical adhesives are prepared from polyisocyanates having the structral formula: <IMAGE> wherein R is a polyvalent aliphatic radical of about 1 to 10 carbon atoms or a polyvalent aromatic radical of 6 to about 24 carbon atoms; A is C, S or P; Z is O or S; Y is 1 when A is C or P, and 2 when A is S; n is 1 or 2; p is at least 1; q is 0 or 1, with the proviso that when A is carbon or sulfur, q is 0; r is 0 or 1, with the proviso that when A is carbon or sulfur, r is 0; X is a residue of an organic compound having active hydrogen-containing groups; and X' is a residue of an organic compound having at least 1 active hydrogen-containing group.
Inventors
- 👤 William D. Fuller
- 👤 Robert K. Blair
- 👤 Murray Goodman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 23:27
CPC Classifications
C; C09; C09J; C09J175/00; A; A61; A61L; A61L24/00; A61L24/04; A61L24/046; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/16; C08G18/18; C08G18/1833; C08G18/20; C08G18/2009; C08G18/2018; C08G18/70; C08G18/72; C08G18/77; C08G18/771; C08G2170/00; C08G2170/60; C08G2230/00
Claims Analysis
Total Claims: 50
Claim 1
Independent Claim
188 words
A method of closing a wound in living tissue which comprises applying to the tissues to be bonded together a curable surgical adhesive comprised of A. a metabolically-acceptable polyisocyanate having the structural formula: ##STR48## wherein R is a polyvalent aliphatic radical of about 1 to 10 carbon atoms or a polyvalent aromatic radical of 6 to about 24 carbon atoms; A is carbon, sulfur or phosphorus; Z is oxygen or sulfur; y is 1 when A is carbon or phosphorus, and 2 when A is sulfur; n is 1 or 2; p is at least 1; q is 0 or 1, with the proviso that when A is carbon or sulfur, q is 0; r is 0 or 1, with the proviso that when A is carbon or sulfur, r is 0; and X is the residue of an organic compound having terminal active hydrogen-containing groups, and X' is a residue of an organic compound having at least 1 active hydrogen-containing group; or B. an excess of said polyisocyanate A above in admixture with an organic compound containing at least two active hydrogen atoms reactive with the polyisocyanate.
Claim 2
Independent Claim
188 words
A method of closing a wound in living tissue which comprises applying to the tissues to be bonded together a curable surgical adhesive comprised of A. a metabolically-acceptable polyisocyanate having the structural formula: ##STR48## wherein R is a polyvalent aliphatic radical of about 1 to 10 carbon atoms or a polyvalent aromatic radical of 6 to about 24 carbon atoms; A is carbon, sulfur or phosphorus; Z is oxygen or sulfur; y is 1 when A is carbon or phosphorus, and 2 when A is sulfur; n is 1 or 2; p is at least 1; q is 0 or 1, with the proviso that when A is carbon or sulfur, q is 0; r is 0 or 1, with the proviso that when A is carbon or sulfur, r is 0; and X is the residue of an organic compound having terminal active hydrogen-containing groups, and X' is a residue of an organic compound having at least 1 active hydrogen-containing group; or B. an excess of said polyisocyanate A above in admixture with an organic compound containing at least two active hydrogen atoms reactive with the polyisocyanate.
Claim 3
Dependent Claim
147 words
A method according to claim 1 wherein the curable surgical adhesive comprises a metabolically-acceptable polyisocyanate having the structure: ##STR49## wherein R is a polyvalent aliphatic radical of about 1 to 10 carbon atoms or a polyvalent aromatic radical of 6 to about 24 carbon atoms; A is carbon, sulfur or phosphorus; Z is oxygen or sulfur; y is 1 when A is carbon or phosphorus, and 2 when A is sulfur; n is 1 or 2; p is at least 1; q is 0 or 1, with the proviso that when A is carbon or sulfur, q is 0; r is 0 or 1, with the proviso that when A is carbon or sulfur, r is 0; and X is the residue of an organic compound having terminal active hydrogen-containing groups; and X' is a residue of an organic compound having at least 1 active hydrogen-containing group.
Claim 4
Dependent Claim
37 words
A method according to claim 1 wherein the curable surgical adhesive comprises an excess of said polyisocyanate from A above in admixture with an organic compound containing at least two active hydrogen atoms reactive with the polyisocyanate.
Claim 5
Dependent Claim
16 words
A method according to claim 1 or 2 wherein the curable surgical adhesive includes a catalyst.
Claim 6
Dependent Claim
13 words
A method according to claim 4 wherein the catalyst is a tertiary amine.
Claim 7
Dependent Claim
113 words
A method according to claim 5 wherein the catalyst is selected from the group consisting of 1,2,4-trimethylpiperazine, N-methylmorpholine, triethylamine, N-(N,N-dimethylaminopropyl)2-pyrollidine, 2,4,6-collidine, pyridine, quinaldine, pyridazine, dibutyltindiacetate, stannous-2-ethylhexanoate, a pyridine carboxylate having the structure: ##STR50## wherein R is lower alkyl, n is 0 to 6 or more; a piperidine carboxylate having the structure: ##STR51## wherein R and n are as defined above, R' is lower alkyl; and an aliphatic amine having the structure: ##STR52## wherein R, R' and R" are lower alkyl; n is as defined above; and an aliphatic amine having the structure: ##STR53## wherein R' is as defined above and R"' is hydrogen or ##STR54## wherein R and n are as defined above.
Claim 8
Dependent Claim
20 words
A method according to claim 1 or 2 wherein in the structural formula, A is carbon and y is 1.
Claim 9
Dependent Claim
20 words
A method according to claim 1 or 2 wherein in the structural formula, A is sulfur and y is 2.
Claim 10
Dependent Claim
20 words
A method according to claim 1 or 2 wherein in the structural formula, A is phosphorus and y is 1.
Claim 11
Dependent Claim
19 words
A method according to claim 1 or 2 wherein in the structural formula, R is a divalent aromatic radical.
Claim 12
Dependent Claim
19 words
A method according to claim 1 or 2 wherein in the structural formula, the divalent aromatic radical is ##STR55##
Claim 13
Dependent Claim
18 words
A method according to claim 1 or 2 wherein in the formula, the divalent aromatic radical is ##STR56##
Claim 14
Dependent Claim
16 words
A method according to claim 1 or 2 wherein in the structural formula, n is 1.
Claim 15
Dependent Claim
16 words
A method according to claim 1 or 2 wherein in the structural formula, n is 2.
Claim 16
Dependent Claim
21 words
A method according to claim 1 or 2 wherein in the structural formula, X is the residue of a hydroxy-terminated polymer.
Claim 17
Dependent Claim
14 words
A method according to claim 15 wherein the hydroxy-terminated polymer is a polymeric polyol.
Claim 18
Dependent Claim
25 words
A method according to claim 16 wherein the polymeric polyol residue is selected from a group consisting of polyester polyol, polyether polyol and polyether/polyester residues.
Claim 19
Dependent Claim
16 words
A method according to claim 17 wherein the polymeric polyol residue is a polyester polyol residue.
Claim 20
Dependent Claim
67 words
A method according to claim 18 wherein the polyester polyol residue has the structure: ##STR57## wherein R 4 and R 5 are aliphatic or aromatic radicals having 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; n is an integer of 0 or 1; c and d are integers of at least 1; and e is an integer of at least 2.
Claim 21
Dependent Claim
58 words
A method according to claim 18 wherein the polyester polyol residue has the structure: ##STR58## wherein R 6 is an aliphatic or aromatic radical having 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; n is an integer of 0 or 1; and f, g, and h are integers of at least 1.
Claim 22
Dependent Claim
16 words
A method according to claim 17 wherein the polymeric polyol residue is a polyether polyol residue.
Claim 23
Dependent Claim
56 words
A method according to claim 21 wherein the polyether polyol residue has the structure: ##STR59## wherein R 3 is an aliphatic or aromatic radical of 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; a is an integer of at least 1; and b is an integer of at least 2.
Claim 24
Dependent Claim
17 words
A method according to claim 17 wherein the polymeric polyol residue is a polyether/polyester polyol copolymer residue.
Claim 25
Dependent Claim
61 words
A method according to claim 23 wherein the polyether/polyester polyol copolymer residue has the structure: ##STR60## wherein R 3 and R 6 are aliphatic or aromatic radicals of 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; m, p, and q are integers of at least 1; and s is an integer of at least 2.
Claim 26
Dependent Claim
23 words
A method according to claim 1 or 2 wherein X in the structural formula is the residue of a polymer containing hydrolyzable linkages.
Claim 27
Dependent Claim
26 words
A method according to claim 1 or 2 wherein X in the structural formula is the residue of a polymer susceptible to cleavage by proteolytic enzymes.
Claim 28
Dependent Claim
15 words
A method according to claim 1 or 2 wherein the polyisocyanate has the formula: ##STR61##
Claim 29
Dependent Claim
15 words
A method according to claim 1 or 2 wherein the polyisocyanate has the formula: ##STR62##
Claim 30
Dependent Claim
83 words
An article of manufacture comprising a two container pack for providing, on mixing of the two components of the pack, a surgical adhesive, which two container pack comprises: in a first container a curable, sterile, polyisocyanate as defined in claim 2 and in a second container an organic compound containing at least two active hydrogen atoms reactive with isocyanate groups of the polyisocyanate, the amount of the polyisocyanate in the first container being in excess of the organic compound in the second container.
Claim 31
Dependent Claim
23 words
The article of manufacture of claim 29 wherein the components in at least one of the containers includes one or more curing catalysts.
Claim 32
Dependent Claim
29 words
An article of manufacture comprising a container for delivering a single-component surgical adhesive which comprises a formulation of at least 1 curable, sterile, polyisocyanate as defined in claim 2.
Claim 33
Dependent Claim
14 words
The article of manufacture of claim 31 wherein the container is a spray container.
Claim 34
Dependent Claim
59 words
An article of manufacture comprising a two container pack for providing on mixing of the two components of the pack, a rapid curing surgical adhesive, which two container pack comprises: in a first container a formulation of at least 1 curable, sterile, polyisocyanate as defined in claim 2 and in a second container a curing catalyst for said polyisocyanate.
Claim 35
Dependent Claim
17 words
The article of manufacture of claim 33 wherein the two component pack is a two component spray.
Claim 36
Dependent Claim
26 words
The articles of manufacture of claims 29, 30, 31, 32, 33, and 34 wherein one or all of the components are dissolved in an appropriate solvent.
Claim 37
Dependent Claim
12 words
The article of manufacture of claim 35 wherein the solvent is dichlorofluoromethane.
Claim 38
Dependent Claim
134 words
A composition comprising a polyisocyanate having the structural formula: ##STR63## wherein R is a polyvalent aliphatic radical of about 1 to 10 carbon atoms or a polyvalent aromatic radical of 6 to about 24 carbon atoms; A is carbon, sulfur or phosphorus: Z is oxygen or sulfur; y is 1 when A is carbon or phosphorus, and 2 when A is sulfur; n is 1 or 2; p is at least 1; q is 0 or 1, with the proviso that when A is carbon or sulfur, 1 is 0; r is 0 or 1, with the proviso that when A is carbon or sulfur, r is 0; X is the residue of a hydroxy-terminated polyester or polyether/polyester; and X' is the residue of an organic compound having at least 1 active hydrogen-containing group.
Claim 39
Dependent Claim
134 words
A composition comprising a polyisocyanate having the structural formula: ##STR63## wherein R is a polyvalent aliphatic radical of about 1 to 10 carbon atoms or a polyvalent aromatic radical of 6 to about 24 carbon atoms; A is carbon, sulfur or phosphorus: Z is oxygen or sulfur; y is 1 when A is carbon or phosphorus, and 2 when A is sulfur; n is 1 or 2; p is at least 1; q is 0 or 1, with the proviso that when A is carbon or sulfur, 1 is 0; r is 0 or 1, with the proviso that when A is carbon or sulfur, r is 0; X is the residue of a hydroxy-terminated polyester or polyether/polyester; and X' is the residue of an organic compound having at least 1 active hydrogen-containing group.
Claim 40
Dependent Claim
67 words
A polyisocyanate according to claim 37 wherein the polyester polyol residue has the structure: ##STR64## wherein R 4 and R 5 are aliphatic or aromatic radicals having 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; n is an integer of 0 to 1; c and d are integers of at least 1; and e is an integer of at least 2.
Claim 41
Dependent Claim
58 words
A polyisocyanate according to claim 37 wherein the polyester polyol residue has the structure: ##STR65## wherein R 6 is an aliphatic or aromatic radical having 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; n is an integer of 0 or 1; and f, g, and h are integers of at least 1.
Claim 42
Dependent Claim
76 words
A polyisocyanate according to claim 37 wherein the polyether/polyester polyol copolymer residue has the structure: ##STR66## wherein R 3 and R 6 are aliphatic radicals of 1 to 12 carbon atoms or aromatic radicals of 6 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; n is an integer of 0 or 1; m, p, and q are integers of at least 1; and s is an integer of at least 2.
Claim 43
Dependent Claim
26 words
A curable polyisocyanate according to claim 40 wherein R 3 is --CH 2 --CH 2 --, R 6 is --CH 2 -- and n is 1.
Claim 44
Dependent Claim
31 words
A curable polyisocyanate according to claim 41 wherein the polyisocyanate has the structure: ##STR67## wherein m is 1 to 10; p is 1 to 20 and q is 1 to 10.
Claim 45
Dependent Claim
22 words
A polyisocyanate according to claim 39 wherein R 6 is --CH 2 --, R 7 is a triol, and n is 1.
Claim 46
Dependent Claim
39 words
A curable polyisocyanate according to claim 43 having the structure: ##STR68## wherein R is hydrogen or lower alkyl; R' is an alkylene of 1 to 4 carbon atoms; n is 1 or 1; and a+b+c is at least 3.
Claim 47
Dependent Claim
76 words
A curable polyisocyanate composition comprising a mixture of 5 to 95% by weight of a polyisocyanate I having the structure: ##STR69## and 5 to 95% of a polyisocyanate II having the structure: ##STR70## wherein R 3 and R 6 are aliphatic or aromatic radicals having 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; f, g, h, m, p, and q are integers of at least 1; and Z is oxygen.
Claim 48
Dependent Claim
76 words
A curable polyisocyanate composition comprising a mixture of 5 to 95% by weight of a polyisocyanate I having the structure: ##STR69## and 5 to 95% of a polyisocyanate II having the structure: ##STR70## wherein R 3 and R 6 are aliphatic or aromatic radicals having 1 to 12 carbon atoms; R 7 is a polyfunctional active hydrogen-containing aliphatic radical; f, g, h, m, p, and q are integers of at least 1; and Z is oxygen.
Claim 49
Dependent Claim
45 words
A curable polyisocyanate composition according to claim 45 wherein polyisocyanate I has the structure: ##STR71## wherein m is 1 to 10; p is 1 to 20, and q is 1 to 10; and polyisocyanate II has the structure: ##STR72## wherein a+b+c is at least 3.
Claim 50
Dependent Claim
26 words
A curable polyisocyanate composition according to claim 46 comprising about 5 to 95% of polyisocyanate I and about 5 to 95% by weight of polyisocyanate II.
References Cited (Backward Citations)
CA673757A
Cited
US3437680A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-05-08 | 1992-11-07 | 1993-05-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-05-08 | 1996-11-07 | 1997-05-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-05-08 | 2000-11-07 | 2001-05-09 | $7700.00 | Window Closed / Lapsed |