WO1992004390A1 - Biostable polyurethane products - Google Patents

Biostable polyurethane products Download PDF

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Publication number
WO1992004390A1
WO1992004390A1 PCT/US1991/006621 US9106621W WO9204390A1 WO 1992004390 A1 WO1992004390 A1 WO 1992004390A1 US 9106621 W US9106621 W US 9106621W WO 9204390 A1 WO9204390 A1 WO 9204390A1
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WO
WIPO (PCT)
Prior art keywords
diisocyanate
aliphatic
glycol
diamine
carbon atoms
Prior art date
Application number
PCT/US1991/006621
Other languages
French (fr)
Inventor
Michael Szycher
Andrew M. Reed
Original Assignee
Polymedica Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polymedica Industries, Inc. filed Critical Polymedica Industries, Inc.
Priority to AU86454/91A priority Critical patent/AU664158B2/en
Publication of WO1992004390A1 publication Critical patent/WO1992004390A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

Definitions

  • This invention relates to polyurethane polymers having a combination of specific properties that makes these polymers especially suitable for long term implementation within a living body.
  • the biostable polymers of tinis invention possess, inter alia, a low modules of elasticity and a high ultimate tensile strength as well as the biostability to permit them to be implanted within a living body and exhibit little or no degradation over extended periods.
  • biodegradation is characterized by the surface fissuring caused by oxidation of the conventional ether linkages present within the polyurethane molecular chain.
  • the oxidation leads to chain cleavage, reduction in molecular weight and eventual catastrophic mechanical failure.
  • Surface fissuring is a progressive phenomenon which starts as surface microfissures which continue to propagate into the bulk, eventually resulting in loss of electrical insulating capacity and inappropriate heart muscle stimulation.
  • the development of a polyurethane polymer in which the onset of microscopic surface fissuring is substantially delayed and/or prevented is desirable to develop improved pacemaker leads.
  • Vascular grafts particularly arterial grafts having diameters of 4 mm or less and suitable for the replacement of coronary arteries, represent a further potential large market for polyurethane polymers if only a suitable material existed. It is generally accepted that dacron and pol tetrafluoroethylene grafts, while having sufficient tensile strength to be suitable for use in large and medium diameter grafts, fails when used as small diameter grafts due to their excessive stiffness, i.e., they do not exhibit a sufficiently low elastic modules. Most currently available polyurethanes, as well as being biodegradable, suffer from a similar problem in that when they have good tensile strengths of about 4500 psi they also have high moduli. There is thus a need for a biostable polyurethane polymer which has both a high tensile strength and a low elastic modules and which can be formed into a small diameter vascular graft.
  • Mammary prostheses today are generally made of a silicone bag containing a silicone gel. In many cases, after a few years, the tissue surrounding these implants stiffens, necessitating surgical removal. One effort to overcome this problem is to wrap a polyurethane foam around the prosthesis to allow tissue ingrowth and thus prevent tissue hardening. The polyurethane foams currently used, however, are known to biodegrade after implantation. Thus, a need exists for the development of
  • SUBSTITUTE SHEET a biostable tissue ingrowth platrorm which has improved cellula infiltration characteristics while simultaneously not being subject to extensive long term biodegradation.
  • the currently used medical polyuretnanes are usually polyether-based polyurethanes in spite of studies which have shown that ether groups especially ethers in which the methyl group is in the alpha position to the ether oxygen is susceptible to in vivo oxidation. Oxidation occurs and causes eventual chain cleavage, leading to significant reductions in molecular weight at the surface and eventual surface fissuring.
  • Polyurethanes made by using lower amounts of the ether component per weight of polymer havin been shown to produ e a polymer having increased bioscability and exhibiting less surface fissuring after implantation for sever months.
  • Biocompatible pol; irethanes soluble in organic solvents are disclosed in Ger. Offen. DE 3, 643,464 (G. Wick, 1988) . These polyurethanes are claimed to be compatible with blood and tissue and useful as catheters, prostheses, and in the production of pacemaker housings.
  • the polyurethanes are produced by reacting an aliphatic or cycloaliphatic macrodiol with 3-33 molar proportion of a cycloaliphatic diisocyanate to give a pre-adduct having NCO groups followed by chain elongation of the pre-adduct with a mixture of the mac -odiol and specific lower aliphatic diol, i.e. trimethylhexanediol.
  • the macrodiol may be 1, 6-hexanediolpolycarbonate.
  • the resultant thermoplastic polymers have tens:'1e strengths of about 4750-5200 psi, moduli of elasticity of about 300 psi or higher, and ultimate elonc ions of about 460-520%.
  • a thin abrasion-resit, nt polyurethane coating for transparent polycarbonate substrates has been prepared by reaction of a polycarbonatediol with an aliphatic diisocyanate and then hardened with a trifunctional crosslinking agent. (Ger. Offen. DE 3,323,684)
  • SUBSTITUTESHEET Polyurethane elastomers for use a coating with superior durability have been prepared from a polyester polyol derived from 1,10- decanedicarboxylic acid and a polycarbonate polyol by reaction with polyisocyanates and optionally with chain extenders. (Japan Kokai 57/31919, 1982)
  • Polycarbonate diols have been used in the manufacture of polycarbonate-polyurethanes for bilayer safety glass automobile windshields by polymerization of an aliphatic diol with a dialkyl carbonate in the present of an alkali metal-free titanium compound. (U.S. 4,1660,853)
  • the biostable polyurethanes of this invention are derived from organic diisocyanates and polycarbonate diols which are chain extended with diamines or mixtures of diamines and alkanolamines, or alkanolamines or with diols.
  • organic diisocyanates and polycarbonate diols which are chain extended with diamines or mixtures of diamines and alkanolamines, or alkanolamines or with diols.
  • aliphatic or cycloaliphatic diisocyanates be used.
  • aromatic diisocyanates and mixtures of aromatic and aliphatic and/or cycloaliphatic diisocyanates may be used.
  • SUBSTITUTE SHEET Biostable polyurethanes which may be steam sterilized can be prepared from an isocyanate terminated prepolymer of an organic diisocyanate and a polycarbonate glycol, which prepolymer is chain extended with a diamine having about 2 to 10 carbon atoms.
  • Biostable polyurethanes can bp repared either via a one shot reaction of an organic diisocyanate, a polycarbonate glycol and a diol having about 2 to 8 carbon atoms or by preparing an isocyanate terminated prepolymer by reaction of an aliphatic or cycloaliphatic diisocyanate with a polycarbonate glycol and chain extending the prepolymer with a diol having about 2 to 8 carbon atoms.
  • the biostable polyurethanes of this invention can be used in the making of films and membrane and also various objects and articles which can be implanted within a living body such as pacemaker, leads, pacemaker bodies, vascular grafts, mammary prostheses, probes, cannulas, cathet. _>rs, artificial organs made from yarns of the invention polyurethanes and the like. It has been found that polyurethanes of the invention are biostable and compatible with tissue and blood; have excellent cellular infiltration characteristics when fashioned into porous structure, such as textile, microporous membrane, etc.; and are resistant to biodegradation. Additionally, the polyurethanes according to the invention have excellent mechanical properties.
  • the present polyurethanes are the reaction productions of an organic diisocyanate or mixtures of organic diisocyanates, a polycarbonate glycol and a diol, a diamine or mixtures of a diamine and are alkanolamine.
  • a diol either a one-shot or prepolymer technique can be used.
  • diamines or mixtures of diamines and alkanolamines either a one-shot
  • SUBSTITUTE SHEET or prepolymer technique may be used but a prepolymer technique is preferably utilized.
  • Diamine-extended polyurethanes have a relatively high urea linkage contents due to their diamine or diamine/alkanolamine extension. This high urea linkage content results in relatively high levels of hydrogen bonding which, in turn, produces strong elastic materials with good flex life properties. This high level of hydrogen bonding also renders the polyurethane pseudocrosslinked or pseudothermosetting.
  • Diol-extended polyurethanes have lower levels of hydrogen bonding which produces polymers having reduced physical properties, such as elongation, ultimate tensile strength, and flex life as compared to the equivalent diamine-extended counterparts. This lower level of hydrogen bonding renders the diol extended polyurethane thermoplastic.
  • Formation of polyurethanes includes reacting the -OH or hydroxyl groups of a polycarbonate glycol with the -NCO or isocyanate groups of an organic diisocyanate in a appropriate equivalent ratio of -NCO groups to - OH groups to form an isocyanate terminated moiety followed by chain extension with a diol, a diamine or a mixture of diamine and alkalamine.
  • the reactions are carried out in the presence of a suitable solvent and under appropriate reaction conditions, although non-solvent reactions can also be carried out.
  • the present polyurethanes can be based on a variety of diisocyanates where the diisocyanate may be represented by the formula OCN-R-NCO wherein R is aliphatic including groups such as aliphatic, aliphatic-alicyclic and aliphatic-aromatic hydrocarbon groups containing from about 4 to 26 carbon atoms, preferably from about 6 to 20 carbon atoms, more preferably from about 6 to 13 carbon atoms or an aromatic group preferably carbocyclic aryl or aralkyl having from about 6 to 14 carbon atoms.
  • R is aliphatic including groups such as aliphatic, aliphatic-alicyclic and aliphatic-aromatic hydrocarbon groups containing from about 4 to 26 carbon atoms, preferably from about 6 to 20 carbon atoms, more preferably from about 6 to 13 carbon atoms or an aromatic group preferably carbocyclic aryl or aralkyl having from about 6 to 14 carbon atoms.
  • diisocyanates include: tetra ethylene diisocyanate, hexamethylene diisocyanate, trimethyl-hexamethylenediisocyanate, tetramethylxylylene c.-isocyanate, 4, 4-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, metaxylene diisocyanate, diethylbenzene diisocyanate, decamethylene 1, 10- diisocyanate, cyclohexylene 1, 2-diisocyanate and cyclohexylene 1, 4-diisocyanate, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; xylene diisocyanate; m-phenylene diisocyanate; hexahydrotolylene diisocyanate (and isomers) , naphthylene-1, 5-diisocyanate
  • the polycarbonate glycols useful in making the present polyurethanes have molecular weight of from about 650 to 3500 molecular weight units' preferabl ___.000 to 2000 molecular weight units and have the following formula
  • F 1 is a linear chain of ab& ⁇ t 2 to 20 carbon atoms.
  • a preferred polycarbonate glycol is hexanediolcarbonate glycol.
  • the diols chain extenders useful in the present invention h ⁇ /e from about 2 to 8 carbon atoms which are preferably in a straight chain with no more than 2 side groups such as methyl or ethyl.
  • diols e hylene glycol, diethylene glycol, triethylene glycol, 1,4- ⁇ utanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2 and 1,3-propylene glycol, 2,3-butylene glycol, dipropylene glycol, dibutylene glycol and mixtures thereof.
  • Suitable alip! tic diamine chain extenders include diamines ha ⁇ e abou 2 to 10 carbon atoms.
  • Exemplary diamines include ethylene diamine, propanediamines, butanediamine, pentanediamine, hexanedimaine, heptanediamine, octanediamine, m-xylylene diamine, l-,4- diaminocyclohexane, 2-methylpentamethylene diamine and mixtures thereof.
  • Suitable alkanola ine chain extenders include ethanolamine and the like.
  • the present polyurethanes can be prepared by reaction of the appropriate reactants in the presence or absence of an inert solvent, preferably under an inert atmosphere at a temperature of from about 50 to 150°C.
  • solvents which may be used are typically polar organic solvents such as, for example, dimethylacetamide, dimethylformamide, tetrahydrofuran, cyclohexanone and 2- pyrrolidone.
  • polyurethanes which are chain extended with diol the preferred equivalent ratio of NCO to hydroxyl of the polycarbonate glycol is from about 1.8 to 2.5 NCO per equivalent of hydroxyl. Approximately one equivalent of diol, diamine or diamine/alkanolamine mixture chain extender is used.
  • the preferred equivalent ratio of NCO to polycarbonate glycol hydroxyl is about 2.8 to 3.2 equivalents NCO to about 1.8 to 2 equivalents of hydroxyl.
  • a monofunctional a ine chain control agent may be employed.
  • a conventional polyurethane such as organometallic compounds may be employed.
  • Illustrative such catalysts are dibutyl tin dilaurate, dioctyl tin dilaurate stannous octoate and zinc octoate.
  • TXDI tetramethylxylylene diisocyanate
  • 1,6-hexaneddiolcarbonate glycol having a molecular weight of 2000 (1.00 equiv.).
  • the temperature is allowed to rise 5 to 110°C. and 0.001% (based on the total weight) dioctyl tin dilaurate (Cotin 430 of Cosan Chemical Cc ) is added. Agitation is begun and the mixture is allowed to react for three hours to form a isocyanate-terminated prepolymer.
  • the prepolymer is then reacted with neopentyl diol (1.0 ⁇ • ° equiv.) at 110°C. for five hours.
  • thermoplastic polyurethane exhibits the following physical properties:
  • the polyurethane is soluble in DMAc, DMF, THF, M- pyrrol, and ethylene chloride. It is insoluble in 0 alcohols, ketones, esters, and aliphatic hydrocarbons.
  • thermoplastic polyurethane exhibits the following physical properties:
  • thermoset polyurethane exhibits the following physical properties:
  • thermoset polyurethane exhibits the following physical properties:
  • thermoplastic polyurethane exhibits the following physical properties:

Abstract

Polyurethane products having long-term biostability in combination with a low modulus of elasticity and a high ultimate tensile strength and other desireable mechanical properties which are particularly useful as leads for implantable pacemakers, as vascular grafts, as mammary prostheses, and as other products which are intended to be placed within the body of a mammal for extended periods with no substantial degradation of the product. The polyurethanes are prepared from the reaction of an organic diisocyanate, preferably an aliphatic or cycloaliphatic diisocyanate with polycarbonate glycol chained extended with diol, diamine or a mixture of diamine and alkanolamine.

Description

BIOSTABLE POLYURETHANE PRODUCTS
BACKGROUND OF THE INVENTION
This invention relates to polyurethane polymers having a combination of specific properties that makes these polymers especially suitable for long term implementation within a living body. The biostable polymers of tinis invention possess, inter alia, a low modules of elasticity and a high ultimate tensile strength as well as the biostability to permit them to be implanted within a living body and exhibit little or no degradation over extended periods.
Extensive investigations have been undertaken over many years to find materials that will be biologically and chemically stable towards body fluids and body tissue. This area of research has become increasingly important with the development of various objects and articles which can be implanted within a living body, such as a pacemaker leads, vascular grafts, mammary prostheses, pacemaker bodies, probes, cannulas, catheters, and the like. Polyurethanes have become particularly crucial in the production of pacemaker leads which provide the pathway for the pacemaker energy output into the heart. The lead insulation may be the most simple looking part of the device, but is one of the most critical components. While it is not unreasonable for a patient to require replacements of the pacemaker energy supply units during his/her life, the insertion of the lead is the more critical portion of the operation and thus must be expected to remain unchanged and provide absolute reliability for periods of 15 years or longer.
Unfortunately, the curr«-.*tly available pacemaker leads are known to biodegrade. The biodegradation is characterized by the surface fissuring caused by oxidation of the conventional ether linkages present within the polyurethane molecular chain. The oxidation leads to chain cleavage, reduction in molecular weight and eventual catastrophic mechanical failure. Surface fissuring is a progressive phenomenon which starts as surface microfissures which continue to propagate into the bulk, eventually resulting in loss of electrical insulating capacity and inappropriate heart muscle stimulation. The development of a polyurethane polymer in which the onset of microscopic surface fissuring is substantially delayed and/or prevented is desirable to develop improved pacemaker leads.
Vascular grafts, particularly arterial grafts having diameters of 4 mm or less and suitable for the replacement of coronary arteries, represent a further potential large market for polyurethane polymers if only a suitable material existed. It is generally accepted that dacron and pol tetrafluoroethylene grafts, while having sufficient tensile strength to be suitable for use in large and medium diameter grafts, fails when used as small diameter grafts due to their excessive stiffness, i.e., they do not exhibit a sufficiently low elastic modules. Most currently available polyurethanes, as well as being biodegradable, suffer from a similar problem in that when they have good tensile strengths of about 4500 psi they also have high moduli. There is thus a need for a biostable polyurethane polymer which has both a high tensile strength and a low elastic modules and which can be formed into a small diameter vascular graft.
Mammary prostheses today are generally made of a silicone bag containing a silicone gel. In many cases, after a few years, the tissue surrounding these implants stiffens, necessitating surgical removal. One effort to overcome this problem is to wrap a polyurethane foam around the prosthesis to allow tissue ingrowth and thus prevent tissue hardening. The polyurethane foams currently used, however, are known to biodegrade after implantation. Thus, a need exists for the development of
SUBSTITUTE SHEET a biostable tissue ingrowth platrorm which has improved cellula infiltration characteristics while simultaneously not being subject to extensive long term biodegradation.
The currently used medical polyuretnanes are usually polyether-based polyurethanes in spite of studies which have shown that ether groups especially ethers in which the methyl group is in the alpha position to the ether oxygen is susceptible to in vivo oxidation. Oxidation occurs and causes eventual chain cleavage, leading to significant reductions in molecular weight at the surface and eventual surface fissuring. Polyurethanes made by using lower amounts of the ether component per weight of polymer havin been shown to produ e a polymer having increased bioscability and exhibiting less surface fissuring after implantation for sever months.
Biocompatible pol; irethanes soluble in organic solvents are disclosed in Ger. Offen. DE 3, 643,464 (G. Wick, 1988) . These polyurethanes are claimed to be compatible with blood and tissue and useful as catheters, prostheses, and in the production of pacemaker housings. The polyurethanes are produced by reacting an aliphatic or cycloaliphatic macrodiol with 3-33 molar proportion of a cycloaliphatic diisocyanate to give a pre-adduct having NCO groups followed by chain elongation of the pre-adduct with a mixture of the mac -odiol and specific lower aliphatic diol, i.e. trimethylhexanediol. The macrodiol may be 1, 6-hexanediolpolycarbonate. The resultant thermoplastic polymers have tens:'1e strengths of about 4750-5200 psi, moduli of elasticity of about 300 psi or higher, and ultimate elonc ions of about 460-520%.
A thin abrasion-resit, nt polyurethane coating for transparent polycarbonate substrates has been prepared by reaction of a polycarbonatediol with an aliphatic diisocyanate and then hardened with a trifunctional crosslinking agent. (Ger. Offen. DE 3,323,684)
SUBSTITUTESHEET Polyurethane elastomers for use a coating with superior durability have been prepared from a polyester polyol derived from 1,10- decanedicarboxylic acid and a polycarbonate polyol by reaction with polyisocyanates and optionally with chain extenders. (Japan Kokai 57/31919, 1982)
Polycarbonate diols have been used in the manufacture of polycarbonate-polyurethanes for bilayer safety glass automobile windshields by polymerization of an aliphatic diol with a dialkyl carbonate in the present of an alkali metal-free titanium compound. (U.S. 4,1660,853)
There exists a substantial need for a family of biostable polyurethane polymers some members of which can be used to produce improved insulating compositions for pacemaker leads, small diameter vascular grafts, and tissue ingrowth platforms having improved cellular infiltration characteristics for mammary prostheses.
It is an object of the present invention to provide such polyurethanes, particularly polyurethanes which may be conventionally steam sterilized.
It is a further object to produce a biostable polyurethane having a tensile strength in excess of 4000 psi and an elastic modules of less than about 200 psi.
SUMMARY OF THE INVENTION
The biostable polyurethanes of this invention are derived from organic diisocyanates and polycarbonate diols which are chain extended with diamines or mixtures of diamines and alkanolamines, or alkanolamines or with diols. When the polyurethane is used in the preparation of long-term internally implanted articles, it is preferred than aliphatic or cycloaliphatic diisocyanates be used. For other applications, aromatic diisocyanates and mixtures of aromatic and aliphatic and/or cycloaliphatic diisocyanates may be used.
SUBSTITUTE SHEET Biostable polyurethanes which may be steam sterilized can be prepared from an isocyanate terminated prepolymer of an organic diisocyanate and a polycarbonate glycol, which prepolymer is chain extended with a diamine having about 2 to 10 carbon atoms.
Biostable polyurethanes can bp repared either via a one shot reaction of an organic diisocyanate, a polycarbonate glycol and a diol having about 2 to 8 carbon atoms or by preparing an isocyanate terminated prepolymer by reaction of an aliphatic or cycloaliphatic diisocyanate with a polycarbonate glycol and chain extending the prepolymer with a diol having about 2 to 8 carbon atoms.
The biostable polyurethanes of this invention can be used in the making of films and membrane and also various objects and articles which can be implanted within a living body such as pacemaker, leads, pacemaker bodies, vascular grafts, mammary prostheses, probes, cannulas, cathet. _>rs, artificial organs made from yarns of the invention polyurethanes and the like. It has been found that polyurethanes of the invention are biostable and compatible with tissue and blood; have excellent cellular infiltration characteristics when fashioned into porous structure, such as textile, microporous membrane, etc.; and are resistant to biodegradation. Additionally, the polyurethanes according to the invention have excellent mechanical properties.
DETAILED DESCRIPTION OF THE INVENTION
The present polyurethanes are the reaction productions of an organic diisocyanate or mixtures of organic diisocyanates, a polycarbonate glycol and a diol, a diamine or mixtures of a diamine and are alkanolamine. When a diol is employed, either a one-shot or prepolymer technique can be used. In the case of diamines or mixtures of diamines and alkanolamines, either a one-shot
SUBSTITUTE SHEET or prepolymer technique may be used but a prepolymer technique is preferably utilized.
Diamine-extended polyurethanes have a relatively high urea linkage contents due to their diamine or diamine/alkanolamine extension. This high urea linkage content results in relatively high levels of hydrogen bonding which, in turn, produces strong elastic materials with good flex life properties. This high level of hydrogen bonding also renders the polyurethane pseudocrosslinked or pseudothermosetting.
Diol-extended polyurethanes have lower levels of hydrogen bonding which produces polymers having reduced physical properties, such as elongation, ultimate tensile strength, and flex life as compared to the equivalent diamine-extended counterparts. This lower level of hydrogen bonding renders the diol extended polyurethane thermoplastic.
Formation of polyurethanes according to this invention includes reacting the -OH or hydroxyl groups of a polycarbonate glycol with the -NCO or isocyanate groups of an organic diisocyanate in a appropriate equivalent ratio of -NCO groups to - OH groups to form an isocyanate terminated moiety followed by chain extension with a diol, a diamine or a mixture of diamine and alkalamine. The reactions are carried out in the presence of a suitable solvent and under appropriate reaction conditions, although non-solvent reactions can also be carried out.
The present polyurethanes can be based on a variety of diisocyanates where the diisocyanate may be represented by the formula OCN-R-NCO wherein R is aliphatic including groups such as aliphatic, aliphatic-alicyclic and aliphatic-aromatic hydrocarbon groups containing from about 4 to 26 carbon atoms, preferably from about 6 to 20 carbon atoms, more preferably from about 6 to 13 carbon atoms or an aromatic group preferably carbocyclic aryl or aralkyl having from about 6 to 14 carbon atoms. Representative examples of such diisocyanates include: tetra ethylene diisocyanate, hexamethylene diisocyanate, trimethyl-hexamethylenediisocyanate, tetramethylxylylene c.-isocyanate, 4, 4-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, metaxylene diisocyanate, diethylbenzene diisocyanate, decamethylene 1, 10- diisocyanate, cyclohexylene 1, 2-diisocyanate and cyclohexylene 1, 4-diisocyanate, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; xylene diisocyanate; m-phenylene diisocyanate; hexahydrotolylene diisocyanate (and isomers) , naphthylene-1, 5-diisocyanate; 1-methoxyphenyl 2,4-diisocyanate diphenylmethane 4,4'-diisocyanate, 4,4*- biphenylene diisocyanate, 3,3-dimethoxy-4, 4-biphenyl diisocyanate; 3,3-dimethyl 4,4' iisocyanate and mixtures thereof.
The polycarbonate glycols useful in making the present polyurethanes have molecular weight of from about 650 to 3500 molecular weight units' preferabl ___.000 to 2000 molecular weight units and have the following formula
0H[R1-0(C0)0-R1] OH in which F1 is a linear chain of ab&αt 2 to 20 carbon atoms. A preferred polycarbonate glycol is hexanediolcarbonate glycol.
The diols chain extenders useful in the present invention hε/e from about 2 to 8 carbon atoms which are preferably in a straight chain with no more than 2 side groups such as methyl or ethyl. The presence of more than two side gro ps, such as methyl or ethyl, is not desired since polyurethanes formed therefrom have lower tensile strengths. Exemplary of these diols are e hylene glycol, diethylene glycol, triethylene glycol, 1,4-^utanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2 and 1,3-propylene glycol, 2,3-butylene glycol, dipropylene glycol, dibutylene glycol and mixtures thereof.
Suitable alip!" tic diamine chain extenders include diamines ha ~e abou 2 to 10 carbon atoms. Exemplary diamines include ethylene diamine, propanediamines, butanediamine, pentanediamine, hexanedimaine, heptanediamine, octanediamine, m-xylylene diamine, l-,4- diaminocyclohexane, 2-methylpentamethylene diamine and mixtures thereof. Suitable alkanola ine chain extenders include ethanolamine and the like.
The present polyurethanes can be prepared by reaction of the appropriate reactants in the presence or absence of an inert solvent, preferably under an inert atmosphere at a temperature of from about 50 to 150°C. Common solvents which may be used are typically polar organic solvents such as, for example, dimethylacetamide, dimethylformamide, tetrahydrofuran, cyclohexanone and 2- pyrrolidone. In polyurethanes which are chain extended with diol, the preferred equivalent ratio of NCO to hydroxyl of the polycarbonate glycol is from about 1.8 to 2.5 NCO per equivalent of hydroxyl. Approximately one equivalent of diol, diamine or diamine/alkanolamine mixture chain extender is used. In polyurethanes which are chain extended with diamine or a diamine/alkanolamine mixture, the preferred equivalent ratio of NCO to polycarbonate glycol hydroxyl is about 2.8 to 3.2 equivalents NCO to about 1.8 to 2 equivalents of hydroxyl.
When diamine or diamine/alkanolamine claim extension is employed a monofunctional a ine chain control agent may be employed.
A conventional polyurethane such as organometallic compounds may be employed. Illustrative such catalysts are dibutyl tin dilaurate, dioctyl tin dilaurate stannous octoate and zinc octoate.
The following examples illustrate typical preparations of polyurethanes embodying the present invention. These examples are illustrative and non- limiting. EXAMPLE I υ
A four liter reactor equipped with continuous nitrogen blanketing and a heating mantel is charged with tetramethylxylylene diisocyanate (TMXDI) (2.1 equiv.), of 1,6-hexaneddiolcarbonate glycol having a molecular weight of 2000 (1.00 equiv.). The temperature is allowed to rise 5 to 110°C. and 0.001% (based on the total weight) dioctyl tin dilaurate (Cotin 430 of Cosan Chemical Cc ) is added. Agitation is begun and the mixture is allowed to react for three hours to form a isocyanate-terminated prepolymer. The prepolymer is then reacted with neopentyl diol (1.0 ^•° equiv.) at 110°C. for five hours.
The resultant thermoplastic polyurethane exhibits the following physical properties:
Ultimate tensile strength 6,100 psi Ultimate elongation 575%
Modulus at 100% strain 300 psi Hardness 65 Shore A
Specific gravity 1.01
The polyurethane is soluble in DMAc, DMF, THF, M- pyrrol, and ethylene chloride. It is insoluble in 0 alcohols, ketones, esters, and aliphatic hydrocarbons.
EXAMPLE II The procedure of Example I is repeated except that the diisocyanate is replaced by 2.1 equiv. of 4,4- dicyclohexylmethane diisocyanate. The resultant thermoplastic polyurethane exhibits the following physical properties:
Ultimate tensile strength 6,400 psi Ultimate elongation 550%
Modulus at 100% strain 310 psi
Hardness 70 Shore A Specific gravity 1.01
SUBSTITUTESHEET EXAMPLE III
The procedure of Example I is repeated except that the diisocyanate and the glycol react in the presence of 1000 ml of tetrahydrofuran and then the neopentyl diol is replaced by 2-methylpentamethylene diamine. The resultant thermoset polyurethane exhibits the following physical properties:
Ultimate tensile strength 4,100 psi Ultimate elongation 675%
Modulus at 100% strain 125 psi Hardness 40 Shore A
Specific gravity 0.35
EXAMPLE IV The procedure of Example III is repeated except that the 2-methylpentamethylene diamine is replaced by ethylene diamine. The resultant thermoset polyurethane exhibits the following physical properties:
Ultimate tensile strength 4,600 psi Ultimate elongation 575%
Modulus at 100% strain 150 psi
Hardness 45 Shore A
Specific gravity 0.35
EXAMPLE V
The procedure of Example II is repeated except that the neopentyl diol is replaced by hexane diol. The resultant thermoplastic polyurethane exhibits the following physical properties:
Ultimate tensile strength 6,100 psi
Ultimate elongation 450%
Modulus at 100% strain 475 psi

Claims

CLAIMS A biostable polyurethane prepared by the reaction of an organic diisocyanate or a mixture of organic diisocyanates, a polycarbonate glycol and an aliphatic diol having about 2 to 8 carbon atoms or an aliphatic diamine having about 2 to 10 carbon atoms or a mixture of an aliphatic diamine having about 2 to 10 carbon atoms and an alkanolamine, or alkanolamines.
A biostable polyurethane ace .rding to claim 1, in which the aliphatic diol having about 2 to 8 carbon atoms has no more than 2 side groups. A biostable polyurethane according to claim 1, wherein the organic diisocyanate is represented by the formula
OCN-R-NCO wherein R is an aliphatic or .omatic group in which the aliphatic group contains from about 4 to 26 carbon atoms and the aromatic group contains from about 6 to 14 carbon atoms.
A biostable polyurethane according to claim 1, wherein the diisocyanate is represented by the formula OCN-R-NCO wherein R is aliphatic, aliphatic- alicyclic or aliphatic-aromatic hydrocarbon containing from about 4 to 26 carbon atoms. A biostable polyurethane according to c^aim 1, wherein the diisocyanate is tetramethylene diisocyanate, hexamethylene di socyanate, trime /l- hexamethylenediisocyanate, tetramethylxylylene diisocyanate, 4, 4-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, metaxylene diisocyanate, diethylbenzene diisocyanate, •- ^camethyxene 1, lO-diisocyanate, cyclohexylene 1, 2- ^xisocyanate, cyclohexylene 1, 4-diisocyanate, or 2,4-toluene diisocyanate; 2,6-2,4-toluene diisocyanate; xylene diisocyanate; m-phenylene
SUBSTITUTE SHEET diisocyanate; hexahydrotolylene diisocyanate (and isomers) , naphthylene-l,5-diisocyanate; 1- methoxyphenyl 2,4-diisocyanate diphenylmethane 4,4'- diisocyanate, 4,4»-biphenylene diisocyanate, 3,3- dimethoxy-4,4-biphenyl diisocyanate; 3,3-dimethyl 4,4' diisocyanate and mixtures thereof.
6. A biostable polyurethane according to claim 1, wherein the polycarbonate glycol has the following formula:
HO[R1-©(CO)O-R1]nOH in which R1 is a linear hydrocarbon chain of about 2 to 20 carbon atoms.
7. A biostable polyurethane according to claim 1, wherein the aliphatic diol is ethylene glycol, diethylene glycol, triethylene glycol, 1,4- butanediol, neopentyl glycol, 1,6-hexanediol, 1,8- octanediol, 1,2 or 1,3-propylene glycol, 2,3-butylene glycol, dipropylene glycol, dibutylene glycol or mixtures thereof.
8. A biostable polyurethane according to claim 1, wherein aliphatic diamine is ethylene diamine, propanediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, m- xylylene diamine, 1,4-diaminocyclohexane, 2- methylpentamethylene diamine or mixtures thereof.
9. A biostable polyurethane according to claim 1, wherein the alkanolamine is ethanolamine.
PCT/US1991/006621 1990-09-12 1991-09-12 Biostable polyurethane products WO1992004390A1 (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0603675A1 (en) * 1992-12-23 1994-06-29 Bayer Ag Catalyst-free polyurethanes
FR2705351A1 (en) * 1993-05-18 1994-11-25 Garcia Alain A method of making and preserving a polymerizable mixture leading to a polyurethane for filling biological cavities.
US5419921A (en) * 1993-03-22 1995-05-30 Medtronic, Inc. Pacing lead insulator
WO1997022643A1 (en) * 1995-12-15 1997-06-26 Artimplant Development Artdev Ab Linear block polymer comprising urea and urethane groups, method for the production of linear block polymers and use of the block polymers as implants
WO1999024084A1 (en) * 1997-11-07 1999-05-20 Salviac Limited Biostable polycarbonate urethane products
EP1066839A1 (en) * 1999-07-08 2001-01-10 Sterilox Medical (Europe) Limited Oxidation-resistant endoscope coatings
US6434430B2 (en) 1999-03-18 2002-08-13 Medtronic, Inc. Co-extruded, multi-lumen medical lead
WO2008153791A1 (en) * 2007-06-08 2008-12-18 Cardiotech International, Inc. Antimicrobial polyurethane resins and products made therefrom
WO2011054932A1 (en) * 2009-11-05 2011-05-12 Nonwotecc Medical Gmbh Non-woven fabric for medical use and process for the preparation thereof

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* Cited by examiner, † Cited by third party
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4160853A (en) * 1976-04-28 1979-07-10 Ppg Industries, Inc. Catalyst for making polycarbonate diols for use in polycarbonate urethanes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3318730A1 (en) * 1983-05-21 1984-11-22 Akzo Gmbh, 5600 Wuppertal Biocompatible polyurethanes
DE3643465A1 (en) * 1986-12-19 1988-07-07 Akzo Gmbh Biocompatible polyurethanes
US4931486A (en) * 1988-12-02 1990-06-05 The Dow Chemical Company Poly(alkylene carbonate) polyols as antistatic additives for polyurethanes
CA2047678A1 (en) * 1989-03-20 1990-09-21 Bert A. Ross Linear polyurethane elastomer compositions and use of modified diisocyanates for preparing same
CA2038605C (en) * 1990-06-15 2000-06-27 Leonard Pinchuk Crack-resistant polycarbonate urethane polymer prostheses and the like

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4160853A (en) * 1976-04-28 1979-07-10 Ppg Industries, Inc. Catalyst for making polycarbonate diols for use in polycarbonate urethanes

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0603675A1 (en) * 1992-12-23 1994-06-29 Bayer Ag Catalyst-free polyurethanes
US5374704A (en) * 1992-12-23 1994-12-20 Bayer Aktiengesellschaft Pure, in particular catalyst-free polyurethanes
US5419921A (en) * 1993-03-22 1995-05-30 Medtronic, Inc. Pacing lead insulator
FR2705351A1 (en) * 1993-05-18 1994-11-25 Garcia Alain A method of making and preserving a polymerizable mixture leading to a polyurethane for filling biological cavities.
EP0626400A1 (en) * 1993-05-18 1994-11-30 Alain Garcia Polymerisalbe composition for surgical or dental use, process for its preparation and dental implant
US6210441B1 (en) * 1995-12-15 2001-04-03 Artimplant Development Artdev Ab Linear block polymer comprising urea and urethane groups, method for the production of linear block polymers and use of the block polymers as implants
AU709440B2 (en) * 1995-12-15 1999-08-26 Artimplant Development Artdev Ab Linear block polymer comprising urea and urethane groups, method for the production of linear block polymers and use of the block polymers as implants
WO1997022643A1 (en) * 1995-12-15 1997-06-26 Artimplant Development Artdev Ab Linear block polymer comprising urea and urethane groups, method for the production of linear block polymers and use of the block polymers as implants
WO1999024084A1 (en) * 1997-11-07 1999-05-20 Salviac Limited Biostable polycarbonate urethane products
US6434430B2 (en) 1999-03-18 2002-08-13 Medtronic, Inc. Co-extruded, multi-lumen medical lead
EP1066839A1 (en) * 1999-07-08 2001-01-10 Sterilox Medical (Europe) Limited Oxidation-resistant endoscope coatings
WO2008153791A1 (en) * 2007-06-08 2008-12-18 Cardiotech International, Inc. Antimicrobial polyurethane resins and products made therefrom
US7772296B2 (en) 2007-06-08 2010-08-10 Advansource Biomaterials Corporation Antimicrobial polyurethane resins and products made therefrom
WO2011054932A1 (en) * 2009-11-05 2011-05-12 Nonwotecc Medical Gmbh Non-woven fabric for medical use and process for the preparation thereof

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CA2091564A1 (en) 1992-03-13
AU8645491A (en) 1992-03-30
EP0548256A4 (en) 1993-07-07
AU664158B2 (en) 1995-11-09

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