US4579879A
Expired / Lapsed
US
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Radiopaque polyurethane-silicone network resin compositions and medical-surgical tubings prepared therefrom
Assignee: Becton Dickinson and Co
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Filing: 1984-06-29
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Granted: 1986-04-01
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Expires: 2004-06-29
Abstract
Abstract This invention relates to novel radiopaque resin compositions, and to medical-surgical tubings and catheters prepared therefrom. More particularly, the invention pertains to compositions of polyiodobenzoic acid ester-containing polyvinyl resins and a platinum-cured silicone network polymer dispersed therein and their use in medical-surgical devices, especially tubing and catheters.
Inventors
- 👤 Vincent J. Flynn
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 14:15
CPC Classifications
C; C08; C08K; C08K5/00; C08K5/04; C08K5/10; C08K5/101; A; A61; A61L; A61L29/00; A61L29/04; A61L29/049; A61L29/14; A61L29/18; C08L; C08L75/00; C08L75/04; A61B; A61B90/00; A61B90/39
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
127 words
A radiopaque composition comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefore consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR8## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b), and, uniformly dispersed therein; (c) a platinum-cured silicone network polymer, the amount of (c) comprising 8 to 30 parts by weight per 100 parts by weight of (a), (b) and (c), wherein said radiopaque composition is essentially free of filler.
Claim 2
Dependent Claim
127 words
A radiopaque composition comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefore consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR8## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b), and, uniformly dispersed therein; (c) a platinum-cured silicone network polymer, the amount of (c) comprising 8 to 30 parts by weight per 100 parts by weight of (a), (b) and (c), wherein said radiopaque composition is essentially free of filler.
Claim 3
Dependent Claim
24 words
A composition as defined in claim 1 wherein, in said radiopacifier (b), each R 1 is iodo and R is (lower)alkyl or (lower)alkoxy (lower)alkyl.
Claim 4
Dependent Claim
14 words
A composition as defined in claim 1 wherein said radiopacifier (b) is n-butyl 2,3,4,6-tetraiodobenzoate.
Claim 5
Dependent Claim
14 words
A composition as defined in claim 1 wherein said radiopacifier (b) is 2-ethoxyethyl 2,5-diiodobenzoate.
Claim 6
Dependent Claim
20 words
A composition as defined in claim 1 wherein said radiopacifier (b) is a mixture of n-butyl 2,3,4,6-tetraiodobenzoate and 2-ethoxyethyl 2,5-diiodobenzoate.
Claim 7
Dependent Claim
14 words
A composition as defined in claim 1 which is essentially free of particulate silica.
Claim 8
Dependent Claim
57 words
A composition as defined in claim 1 wherein said platinum-cured silicone network polymer (c) comprises the reaction product of (i) an organic silicon compound having at least two silicon-bonded unsaturated groups per molecule, (ii) a silicon compound containing at least two silicon-bonded hydrogen atoms per molecule, and (iii) a small, catalytically effective amount of a platinum-containing catalyst.
Claim 9
Dependent Claim
98 words
A composition as defined in claim 7 wherein component (i) is of the formula: ##STR9## and component (ii) is of the formula: ##STR10## where R is selected from monovalent hydrocarbon radicals free of olefinic unsaturation, halogenated monovalent hydrocarbon radicals free of olefinic unsaturation, cyanoalkyl radicals or a mixture of any of the foregoing; R 1 is selected from vinyl radicals, allyl radicals or a mixture thereof; a has a value of from 1.0 to 2.5; b has a value of from 0.005 to 2.0; and the sum of a plus b is equal to from 1.005 to 3.0.
Claim 10
Dependent Claim
36 words
A composition as defined in claim 8 wherein component (iii) is selected from chloroplatinic acid, platinum black, platinum adsorbed on a carrier, a platinum-olefin complex, a platinum-cyclopropane complex or a mixture of any of the foregoing.
Claim 11
Dependent Claim
282 words
A two part composition adapted for melt blending and thermoforming into radiopaque tubing, Part A comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR11## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b), and (c)(i) an organic silicon compound having at least two silicon-bonded unsaturated groups per molecule; and Part B comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR12## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); (c)(ii) a silicon compound containing at least two silicon-bonded hydrogen atoms per molecule; and (c)(iii) a small, catalytically effective amount of a platinum-containing catalyst, wherein the respective amounts of (c)(i), (ii) and (iii) are selected to provide from about 8 to about 30 parts by weight of a platinum-cured silicone network polymer, after having blended and thermoformed parts A and B, per 100 parts by weight of the total composition, and wherein said two part composition is essentially free of filler.
Claim 12
Dependent Claim
282 words
A two part composition adapted for melt blending and thermoforming into radiopaque tubing, Part A comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR11## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b), and (c)(i) an organic silicon compound having at least two silicon-bonded unsaturated groups per molecule; and Part B comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR12## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); (c)(ii) a silicon compound containing at least two silicon-bonded hydrogen atoms per molecule; and (c)(iii) a small, catalytically effective amount of a platinum-containing catalyst, wherein the respective amounts of (c)(i), (ii) and (iii) are selected to provide from about 8 to about 30 parts by weight of a platinum-cured silicone network polymer, after having blended and thermoformed parts A and B, per 100 parts by weight of the total composition, and wherein said two part composition is essentially free of filler.
Claim 13
Dependent Claim
24 words
A two-part composition as defined in claim 10 wherein, in said radiopacifier (b), each R 1 is iodo and R is (lower)alkyl or (lower)alkoxy(lower)alkyl.
Claim 14
Dependent Claim
25 words
A two-part composition as defined in claim 10 wherein said radiopacifier (b) is selected from n-butyl 2,3,4,6-tetraiodobenzoate, 2-ethoxyethyl 2,5-diiodobenzoate or a mixture of the foregoing.
Claim 15
Dependent Claim
15 words
A two-part composition as defined in claim 10 which is essentially free of particulate silica.
Claim 16
Dependent Claim
107 words
A two part composition as defined in claim 10 wherein component (c)(i) of Part A is of the formula: ##STR13## and component (c)(ii) of Part B is of the formula: ##STR14## where R is selected from monovalent hydrocarbon radicals free of olefinic unsaturation, halogenated monovalent hydrocarbon radicals free of olefinic unsaturation and cyanoalkyl radicals or a mixture of any of the foregoing; R 1 is selected from vinyl radicals, allyl radicals or a mixture thereof; a has a value of from 1.0 to 2.5; b has a value of from 0.005 to 2.0; and the sum of a plus b is equal to from 1.005 to 3.0.
Claim 17
Dependent Claim
37 words
A two-part composition as defined in claim 14 wherein component (c)(iii) is selected from chloroplatinic acid, platinum black, platinum adsorbed on a carrier, a platinum-olefin complex, a platinum-cyclopropane complex or a mixture of any of the foregoing.
Claim 18
Dependent Claim
127 words
Medical-surgical tubing comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR15## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier (b) comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); and, uniformly dispersed therein, (c) a platinum-cured silicone network polymer, the amount of (c) comprising 8 to 30 parts by weight per 100 parts by weight of (a), (b) and (c), wherein said medical-surgical tubing is essentially free of filler.
Claim 19
Dependent Claim
127 words
Medical-surgical tubing comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR15## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier (b) comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); and, uniformly dispersed therein, (c) a platinum-cured silicone network polymer, the amount of (c) comprising 8 to 30 parts by weight per 100 parts by weight of (a), (b) and (c), wherein said medical-surgical tubing is essentially free of filler.
Claim 20
Dependent Claim
23 words
Medical-surgical tubing as defined in claim 16 wherein, in said radiopacifier (b), each R 1 is iodo and R is (lower)alkyl or (lower)alkoxy(lower)alkyl.
Claim 21
Dependent Claim
14 words
Medical-surgicial tubing as defined in claim 16 wherein said radiopacifier (b) is n-butyl 2,3,4,6-tetraiodobenzoate.
Claim 22
Dependent Claim
14 words
Medical-surgical tubing as defined in claim 16 wherein said radiopacifier (b) is 2-ethoxyethyl 2,5-diiodobenzoate.
Claim 23
Dependent Claim
20 words
Medical-surgical tubing as defined in claim 16 wherein said radiopacifier (b) is a mixture of n-butyl 2,3,4,6-tetraiodobenzoate and 2-ethoxyethyl 2,5-diiodobenzoate.
Claim 24
Dependent Claim
43 words
Medical-surgical tubing as defined in claim 16 which also includes as a partial replacement for said radiopacifier (b) a compound selected from bismuth oxychloride or barium sulfate in an amount sufficient to enhance the radiopacity of said tubing while maintaining its tensile strength.
Claim 25
Dependent Claim
14 words
Medical-surgical tubing as defined in claim 16 which is essentially free of particulate silica.
Claim 26
Dependent Claim
57 words
Medical-surgical tubing as defined in claim 16 wherein said platinum-cured silicone network polymer (c) comprises the reaction product of: (i) an organic silicon compound having at least two silicon-bonded unsaturated groups per molecule, (ii) a silicon compound containing at least two silicon-bonded hydrogen atoms per molecule, and (iii) a small, catalytically effective amount of a platinum-containing catalyst.
Claim 27
Dependent Claim
99 words
Medical-surgical tubing as defined in claim 23 wherein component (i) is of the formula: ##STR16## and component (ii) is of the formula: ##STR17## where R is selected from monovalent hydrocarbon radicals free of olefinic unsaturation, halogenated monovalent hydrocarbon radicals free of olefinic unsaturation and cyanoalkyl radicals or a mixture of any of the foregoing; R 1 is selected from vinyl radicals, allyl radicals or a mixture thereof; a has a value of from 1.0 to 2.5; b has a value of from 0.005 to 2.0; and the sum of a plus b is equal to from 1.005 to 3.0.
Claim 28
Dependent Claim
36 words
Medical-surgical tubing as defined in claim 24 wherein component (iii) is selected from chloroplatinic acid, platinum black, platinum adsorbed on a carrier, a platinum-olefin complex, a platinum cyclopropane-complex or a mixture of any of the foregoing.
Claim 29
Independent Claim
286 words
A method for the production of radiopaque medical-surgical tubing, said method comprising: (1) providing a two-part composition which is essentially free of filler, Part A comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR18## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); and (c)(i) an organic silicon compound having at least two silicon-bonded unsaturated groups per molecule; and Part B comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diidobenzoate or a tetraiodobenzoate compound of the formula: ##STR19## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); (c)(ii) a silicon compound containing at least two silicon-bonded hydrogen atoms per molecule; and (c)(iii) a small, catalytically effective amount of a platinum-containing catalyst, the respective amounts of (c)(i), (ii) and (iii) being selected to provide from 8 to 30 parts by weight of a platinum-silicone network polymer per 100 parts by weight of the total composition; (2) melt blending Part A and Part B, and (3) extruding the blended mixture of (2) into tubing.
Claim 30
Independent Claim
286 words
A method for the production of radiopaque medical-surgical tubing, said method comprising: (1) providing a two-part composition which is essentially free of filler, Part A comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diiodobenzoate or a tetraiodobenzoate compound of the formula: ##STR18## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); and (c)(i) an organic silicon compound having at least two silicon-bonded unsaturated groups per molecule; and Part B comprising: (a) a resin which includes from 100 to 33 parts by weight of a thermoplastic polyurethane and from 0 to 67 parts of a polymer of a halogenated vinyl monomer; (b) a radiopacifier therefor consisting of a diidobenzoate or a tetraiodobenzoate compound of the formula: ##STR19## wherein R 1 is hydrogen or iodo, and R is alkyl or alkoxyalkyl or a mixture of said compounds, said radiopacifier comprising 10 to 40 parts by weight per 100 parts by weight of (a) and (b); (c)(ii) a silicon compound containing at least two silicon-bonded hydrogen atoms per molecule; and (c)(iii) a small, catalytically effective amount of a platinum-containing catalyst, the respective amounts of (c)(i), (ii) and (iii) being selected to provide from 8 to 30 parts by weight of a platinum-silicone network polymer per 100 parts by weight of the total composition; (2) melt blending Part A and Part B, and (3) extruding the blended mixture of (2) into tubing.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1989-03-31 | 1989-09-30 | 1990-04-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-03-31 | 1993-09-30 | 1994-04-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-03-31 | 1997-09-30 | 1998-04-01 | $7700.00 | Window Closed / Lapsed |