CA1134088A - Silicone-containing thermoplastic polymers for medical uses - Google Patents
Silicone-containing thermoplastic polymers for medical usesInfo
- Publication number
- CA1134088A CA1134088A CA321,982A CA321982A CA1134088A CA 1134088 A CA1134088 A CA 1134088A CA 321982 A CA321982 A CA 321982A CA 1134088 A CA1134088 A CA 1134088A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/049—Mixtures of macromolecular compounds
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- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
- A61L29/18—Materials at least partially X-ray or laser opaque
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M25/00—Catheters; Hollow probes
- A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
- A61M25/0105—Steering means as part of the catheter or advancing means; Markers for positioning
- A61M25/0108—Steering means as part of the catheter or advancing means; Markers for positioning using radio-opaque or ultrasound markers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S128/00—Surgery
- Y10S128/21—Silicone
Abstract
ABSTRACT OF THE DISCLOSURE
A flexible composition which is preferably radio-paque comprises a plastic material which may be mixed with from 10 to 50 percent by weight of a radiopaque filler.
The plastic material comprises the product of (a) block copolymer having thermoplastic, rubbery characteristics, having a central rubbery olefin block and terminal blocks of a polystyrene; (b) low crystallinity ethylene polymers such as poly (ethylene-vinyl acetate); and (c) a silicone gum containing a small amount of a silicon-bonded olefin group such as vinyl. Optionally, the addition of 5 to 40 percent by weight polypropylene may be included in these materials to improve their heat resistance and strength without affecting their transparency, when transparent materials are formulated.
A flexible composition which is preferably radio-paque comprises a plastic material which may be mixed with from 10 to 50 percent by weight of a radiopaque filler.
The plastic material comprises the product of (a) block copolymer having thermoplastic, rubbery characteristics, having a central rubbery olefin block and terminal blocks of a polystyrene; (b) low crystallinity ethylene polymers such as poly (ethylene-vinyl acetate); and (c) a silicone gum containing a small amount of a silicon-bonded olefin group such as vinyl. Optionally, the addition of 5 to 40 percent by weight polypropylene may be included in these materials to improve their heat resistance and strength without affecting their transparency, when transparent materials are formulated.
Description
~L3~3~
BACKGROUND OF THE INVENTION
.
Silicones, particularly polymers and copolymers o dimethylpolysiloxane, are used in numerous medical devices because of the known compatibility of the mater-ials to living ~issue. ~owever, a drawback for the wider usage of silicone in the medical field is ~hat it is expensive, and of relatively low tensile strength when compared with many other ~lexible plastic materials.
Accordingly, there is a need for stronger, less expensive materials than silicone; which at the same time exhibit equivalent tissue compatibility and non-clotting characteristics to silicone materials so that they may be used to make, for example, intravenous catheters de-signed for long-term retention in position of communica-tion with a blood vessel for the administration of parenteral solutions and ~he like.
Grat polymers including silicone materials are known, as described for example in U.S. Patent No.
3~865,897~ In this patent, graft polymers of silicone yum5 with polyethylene, polymethylpentene, polypropylene, and a copolymer of tetra~luorethylene repeating units ~nd ethylene repeating units are disclosed, along with the teaching of how to graft them by placing them under shearing mixing conditions at elevated temperatures.
More details with respect to silicone-poly-ethylene blends are disclosed in the article entitled Sillcone Polyethylene Blends by James R. Falender, et al '~
in Polymer Engineering and Science, Vol. 16, No. 1, January, 1976. However, ~he materials of this type which have been tested have not exhlbited satisfactory melt processability to get a smooth surface, or the desired higher ultimate strength and elastic behavior which would be desired for an intravenous catheter or a blood bag, for example.
Also, it is usually desired for intravenous catheters, in particular, to be radiopaque for purposes o visualization of the catheter on an X-ray fluoroscope or the like. However, silicone catheters which contain enough of a radiopaque filler such as barium sulfate to be strongly radiopaque may be of very low tensile strength.
Polytetrafluoroethylene catheters and catheters made of many other matexials which contain E~ high level of such a radiopaque filler, become unduly stiff.
Accordingly, there is a need for a flexible, plastic material which is relativelv non-clotting and highly tissue compatible, and which can also remain fIex-~0 ible and strong at a high loading of radiopaque iller, forexample on the order of 10 to 50 percent by weight.
~ he formulations of this invention exhibit good compatibility with tissue, reducing the normal irritation of tissue in the presence o a foreign material. Also they have low thrombogenicity, and thus can be used in longer~term contact with blood. Furthermore, the mater-ials of t~is invention can remain relatively flexible and strong, when compared with other medical materials, even when loaded with extraordinarily high amounts of a radiopaque filler such as barium sulfate. Accordingly, tissue-compatible catheters for long-term implantation, and particularly, radiopaque catheters are advantageously made by this present invention.
DESCRIPTION OF THE INVENTION
In accordance with this invention, a flexible composition is provided, being made of a plastic material which comprises (a) from 30 to 50 percent by weight of a block copolymer having thermoplastic rubber characteris-tics and having a central block of a rubbery polyolefin, and terminal blocks of a polystyrene; (b) from 30 to 50 percent by weight of a thermoplastic low crystallinity ethylene polymer such as those selected from the group consisting of poly(ethylene-vinyl acetate) containing rom 0 to 35 percent by weight of vinyl acetate units, or a low - crystallinity polymer of e~hylene containing from 0 to 60 percent by weight of propylene units, and having a molecular weight of at least about 10,000; and (c) from 2 to 30 percent by weight of a cross-linked silicone gum consisting of essen tially of (R2SiO) units, in w~ich R is selected from the group consisting of methyl, phenyl, vinyl, and allyl, at least half of said R groups being methyl, and from 0.5 to 10 mole percent of said R groups being vinyl or allyl prior to crosslinking. The above percentages are calculated with-out regard to filler or other ingredients present apart from 3~3 (a) and (b). Furthermore, we have discovered that the materials of this invention, when containing submicroscopic silica ~iller in conjunction with phenyl-containing sili-cones, are transparent at unexpectedly high levels of silicone and low levels of phanyl-group content.
The above-described materials have been found to be capable of accepting remarkably high loadings of radio-paque filler such as baxi~n sulfate, for example, 10 to 50 percent by weight, while retaining adequate tissue com-patibility, tensile strength, softness, and flexibility,unlike other known medical polymers. Accordingly, a tissue compatible, flexible catheter can be obtained which may be highly radiopaque, for example, I.V. catheters, cen-tral veinous catheters and Foley Catheters. The material may also be used for other medical uses such as blood or platelet bags, where a non-radiopaqu~e material of this in-vention may be used. Particularly, a most desirable intra-venous catheter may be made from the material of this inven-tion, such as a central veinous catheter capable of long-term emplacement for well in excess of a week without ex-cessi~e blood clotting and ~issue trauma.
It is generally preferred for about 20 to 40 percent of barium sulfate or other filler to be present as the radiopaque filler in the plastic material of this in-vention~ However, other radiopaque fillers such as iodine-containing organic compounds, tungsten powder, or bismuth trioxide may also be used as partial or complete substi-tutes for the barium sulfate, in appropriate circumstances.
Ingredient ~a), which is the block copolymer having thermoplastic rubber characteristics, is commer~
cially available in various types and grades, for example, from the Shell Chemical Company under the trademark "KRATON", or from the Phillips Chemical Company under the trademark "SOLPRENE". The rubbery olefin central block may consist of such matexials such polybutadiene, polyisoprene, or poly (ethylene~butylene), the latter being generally pxeferred.
If desired, chain branching units and the like may also be included.
The rigid, usually terminal blocks of ingredient (a) customarily consist of polystyrene, although it is con-templated that derivatives of polystyrene and other e~ui-valent materials can be used as wel:L. Preferably, the Brookield viscosity of ingredient ~a) is 10 to 2000 cps., as a 10 weight percent toluene solution, measured at 25 C.
As ingredient (b), the poLy(ethylene-vinyl ace-tate) preferably contains on the order of 25 to 30 percent by weigh~ of vinyl acetate uni~s, and is a ~hermoplasti polymer. Ingredient (b) serves as flow aid for extrusion of the material of this invention/ and also serves to help provide a more flexible material, even in the presence of the high filler loading~ contemplated in the preferred embodiments. The stiffness of the material of this inven-~5 tion can be controlled to some extent by adjusting thexelative amounts of ingredients (a) and (b), ingredient (b) being of relatively low cost. Also, inyredient ~b) can im-prove the grafting prccess of making these materials.
~39~
Ingredient (b) may also include generally low crystallinity polymers of principally ethylene, preferably having a molecular weight of at least 10,000, for example, low density polyethylene (e.g., a density of about 0.91 to 0.935 g/cc) and copol~mers of ethylene containing up to 60 mole percent of co-polymerized propylene units, in which case the material is known as poly(ethylene-propy-lene).
PreEerably, ingredients (a) and (b), along with any filler that is included, may be initially mixed, for example in a Brabender mixing chamber at a chamber temper~
ature of approximately 190 C.. The chamber is preerably flushed with nitrogen to eliminate oxygen.
Thereafter, ingredient (c), the silicone gum, may be added, and mixed with shearing action at a temperature typically of at least 190 C., although lower temperatures can be used with larger volume mixing equipment, on the order of 150 pounds of ingredients or the like, in which higher shear stresses are obtained in the mixing chamber.
Under these conditions, a crosslinking reaction is belie~ed to ta~e place in the silicone gum, to greatly reduce its migration from the final product plastic material. Also, a grafting reaction may take place under certain circum-stances between the silicone gum and ingredients (a) or (b). These chemical reactions create a strengthened, flexible, elastomeric material having the desired charac-teristics specified above.
The silicone gum, ingredient (c), is preferably present in a concentration of about 5 to 20 percent by weight, without regard to filler or other ingredients than (a) and (b) present, for example, about lO percent by 5 weight. Typically, the silicone gum ma~T have a molecular weight on the order of at least about 70,000 and preferably higher to render the silicone nonextractable from the com-pleted material, and preferably contains a majority o~
dimethylsiloxane tmits so that R as defined above is pre-dominantly meth~l. However, as an alternative, phenylmethyl-siloxane and diphenylsiloxane units may also be included, along with other equivalent siloxane units that do not sig-nificantly chanye the properties of the material, when and as desired. Branched chain siloxane. gums may also be used.
As stated above, in the si.licone gum, from essen-tially 0.5 to 10 mole percent of the R groups should be vinyl or allyl, pre~erably 3 to 6 mole percent, with vinyl groups being localized in blocks or clusters in the mole-cule, in order to impart more completely the desirable properties of silicone to the completed material. These are preferably provided in the form of vinylmethylsiloxane units, although vinyl-containing siloxane units such as divinyl ~iloxane, allylmethylsiloxane, or trivinyl siloxane units may be also used in equivalent quantities.
Alternatively, silicone-bonded reactive groups can be used in combination with or as a substitute for alkenyl groups. For example, silicone gums with Si-H units can crosslink with silicon-bonded vinyl-containing gums, especially in the presence of platinum catalysts. The various other well known crosslinking systems for silicone gums may also be used in appropriate circumstances, such as silicones with attached groups of acetoxy, hydroxy, ethoxy, methoxy and acryloxypropyl siloxane.
The silicone gum provides a surprising degree of softness and flexibility to the finished product, especially at high filler loadings. Surprisingly, silicone gum gener-ally, when mixed in small amounts such as 5 to 30 weight percent with other organic polymers of higher tensile strength, provides a softer material capable of acc~ptiny larger amounts of fillers, and particularly barium sulfate, than the silicone-free organic polymers.
Preferably, 40 to 50 percent by weight each of ingredients (a~ and (b) may be present in the pure plastic material of this invention, while from 8 to 15 percent by weight of ingredient (c) may be present, without regard to filler or other ingredients than (a) and (b) present.
While not wishing to be restricted to any theory of operation of the synthesis of the ~ormulation of this 2Q invention, it is believed that ~he vinyl or allyl groups on the silicone molecule particip~te in a crosslinking or grafting process to provide the finished product claimed in this inventionr Other materials may be added to the formulation of this invention as desired. For example, a reinforcing type submicroscopic silica filler may be utilized, espec-ially when silane-treated for compatibility with the polymer.
However/ it has been generally found that increased amounts of ingredient (c), the silicone gum, are needed in this circumstance because of the strong affini-ty of silane-txeated reinforcing silica filler for the silicone gum.
The incorporation of submicroscopic silica into transparent embodiments of the invention of this application permits the addition of larger amounts of silicones, and silicones at lower refractive index, while retaining transparency.
Other materials such as antioxidants, pigments, and the like may be added as well, but the formulation of this in~ention is preferably free of leachable liquid componen-ts such as oil plasticizers.
~ eat resistance, strength, and stiffness may be increased by adding 5 to 40 percent by weight of highly crystalline polyolefins, such as polypropylene, poly-methylpentene, polyethylene and copolymers of such r without necessarily diminishing the transparency of those composi-tions which are transparent without this addition.
Particularly, when highly crystalline polyolefins are used, it is generally preferred to use from 5 to 25 percent by weight of such a material, for example, poly-propylene, the percentage being based on the entire weightof the composition.
When submicroscopic or fume silica is used, it is generally preferred that approximately from 10 to 30 percent by weight be present, based upon the weight of the entire composition, In this preferred composition at least 10 mole percent of the R groups present in the crosslinkable silicone gum are phenyl groups, It has been particularly found that when clear compositions in accordance with this invention are desired to be used, the use of phenyl-containing silicone compositions tend to improve the clarity. It has been found that when fume silica is used as a filler, equal clarity in a compo-sition can be achieved while using a silicone composition having a lower phenyl content, which is generally a less expensive material.
In the drawings, ~igure 1 is a perspective view of a central veinous catheter made in accordance with this invention.
Figure 2 is a perspective view of the central veinous catheter of this invention shown emplaced in a patient.
Referring to the drawings, the central veinous catheter 10 comprises a flexible, tubular shaft 12 which may be made of the elastomeric material of this invention, and a conventional hub 13 at one end thereof, which may be made of any desired plastic material. Hub 13 is pro-vidPd as a connector member ~or other parts, and may also be used as a suturing site to prevent withdrawing of the catheters, as is conventionally known.
As shown in Figure 2, the catheter of this in-2Q vention may be inserted into a vein of a patient by being pas~ed through a relatlvely short introducer catheter 14 which, in turn, carries at its end a hub 16. A connection from a parenteral solution source or the like may then communicate thorugh the bore of hub 16 to provide ~luid connection through hub 13 and catheter 12.
The above catheter system may be similar to the CENTRASIL T-~- silicone elastomer central veinous catheter which is currently sold by the Vicra Division o Travenol Laboratories, Inc., Dallas, Texas, with the material of ~L3~
catheter shaft 12 being m~e in accordance with this in-vention for yood flexibility, softness, kink resistance, thrombo-resistance, high strength, and low friction, in conjunction with good visibility by X-ray.
`'~ Catheter guard 18 is placed near the front end ~, ,, ~ o~ introducer catheter 14 after the emplacement of central : veinous catheter 12, with the introducer catheter 14 beiny withdrawn out of the central vein, but its tip is still allowed to remain in subcutaneous position in the ~l0 final emplacement. This reduces the possibility of irri-tation to the vein.
~- The exarnples below are providèd for illustrative purposes only, and are not intended to limit the scope of the invention of this application, which is as defined in the claims below.
..
Example 1. To a Brabender ~lasticorder, Model MV100, with an attached mixing/measuring head, purged with nitrogen gas and heated to 195 C., was added (a) 13.5 grams of a block copolymer (KR~TON G1662) having thermo-'0 plastic rubber characteristics, with a central block of - ethylene and butylene copolymer units in generally equal molar proportions, and terminal blocks of polystyrene, in which the ethylene-butylene portion of the copolymer comprises about 70 percent by weight of the copolymer mole-cule, and the material has a Brookfield viscosity at 25 C.
of 20 cps.~ using a 10 weight pexcent solution in toluene, and containing from 0.03 to 0.07 percent by weight of A0330 antioxidant (sold by Ethyl Corporation); (b3 13.5 grams of * Trademark ~, .
poly(ethylene-virlyl ac~tate) having a vlnyl acetate content of 28 percent and a melt index of 3.5, as tested by ASTM
test D-1238-73, condition E, (Ultrathene UE 634-00, sold by U.S. Industries); and 12 ~ 8 grams of finely powdered barium sulfate (Blanc Fixe XR [Barium Sulfate XR] sold by the Ore and Chemical Co.).
This mixture was mixed in the Brabender device fox two minutes under a nitrogen atmosphere. Following this, 3.0 grams of (c) a dimethylpolysiloxane gum contain-. !0 ing approximately 5 weight percent of methylvinylsiloxaneunits (Union Carbide Y8203 or Rhodia Co. RC356) was added.
The Brabender fixed cam blade rotor type mixing chamber was brought to a ~inal temperature of 225Co while exert-ing maximum torque in the shearing mixing. The reaction 5 time to maximum torque was 2.7 minutes, followed by a mixing time of 3.3 minutes. The initial torque was 2150 meter-grams, and the final torque 2245 meter-grams. The final temperature of the material processed was 238 C. with the Brabender - mixing rotors rotating at 190 r.p.m.
~0 The above pxocess was repeated on fifteen separ-ate occasions to provide sufficient material or extru-sion of a tube. Therea~ter, a tube having a bore diameter of approximately 0.035 inch and an outer diameter of 0.065 inch was extruded out of the material. The extruded tubing ~25 was cut into 21 inch lengths, and hubs were attached to the tubing as illustrated in the drawing and described above, for providing central veinous catheters.
- 13 ~
* Trademark The resultin-3 central veinous catheters exhibit excellent tissue compatibility, as illustrated by super-ior nonthrombogenic charac-teristics of the type generally exhibitecl by silicone rubber. The catheters were flexible and highly radiopaque, while retaining improved tensile strength, lower friction, and were easier to maintain free of attracted dust and the like, compared with pure silicone catheters having similar or lesser amounts of barium sul-fate or tungsten as a filler.
LO Example 2. To the previous Brabender mixin~ de-vice, purged with nitrogen gas, and heated to 195 C. was :: *
added (a) 40 parts by weight of a block copolymer (KRATON
Gl650) having thermoplastic rubber characteristics with a central block of ethylene and butylene copolymer units in L5 equal molar portions, and terminal blocks of polystyrene, the material having a Brookfield viscosity of 1,500 cps.
at 20 weight percent in toluene at 77 F.; 40 parts by weight o~ (b) a poly(ethylene-vinyl acetate) thermoplastic having 28 percent by weight of vinyl acetate units and a melt index of 1.5 (Union Caxbide DQDA2803). These materials were mixed in the Brabender mixing chamber in pelletized - form under nitrogen at 140 r.p.m. No filler was usedO
Thereafter, 20 parts by weight of (c) a soft sili-cone gum (General Electric 449-336-15) having a viscosity ~5 of 55 million centipois~ at 25 C. and containing 4 mole percent vinylmethylsiloxane units, 20 mole percent diphenyl siloxane units, and essentially the balance being dimethyl-siloxane units, were added to provide a 40 gram batch in * Trademark ,, .
~ 3 ~
khe compoundillg machine. Tl-e machine was operated for four rninutes under nitrogen at 140 r.p.m. in a mixing and purge cycle, and therea~ter for four minutes for completion of the grafting process~ The initial torque was 1720 metex-grams, and a final torque of 2480 meter-grams. The initial oil temperature of the compounding machine was 208 C. and - the final temperature of the material processor was 239 C.
Thereafter, the material was allowed to cool for 1 1/2 minutes under nitrogen at 20 r.p.m., removed and ex-L0 truded as tubing which ~-as strong, soft, kink-resistant, heat sealable, having good thromboresistant characteristics and improved transparency for viewing blood.
The refractive index of the silicone material is selected to essentially match the reEractive index o~ the other ingredients for improved clarity.
Addition of 10 weight percent polypropylene (Rexene 23M2, made by Rexene Polyolefins Co.) having a melt flow rate of 2.0 and a density of 0.895 g/cc provides a transparent material also capable of steam sterilization.
It has high gas permeability, which is advan~ageous for storing blood components, especially platelets.
Example 3. The formulation of Example 1 was prepared; enough barium sulfate radiopaque filler was added to provide a formulation in which the amount of barium sul-fate present was 40 percent by weight of the amount ofplastic material. The resulting product still exhibited acceptable flexibility, kink-resistance, strength, and thrombo-resistance, although showing slightly more trauma to the inside blood vessel wall~
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Exam~le 4. The process o~ Example 2 was repeated, utilizing 45 percent by weight of khe ICRATON G1650 material for ingredient (a); 45 pexcent o the same ethylene vinyl acetate copolymer ~or ingredient (b), and using no filler.
After initial mixing under a nitrogen purge in the Braben-der blending device,l0 percent by weight of Union Carbide W980 silicone ~um was added, being a random copolymer gum of dimethylsiloxane units and 3.5 weight percent methyl-vinylsiloxane units, and end blocked with trimethylsiloxane Q0 units.
The mixture was fluxed at 140 r.p.m. under nitro-gen for 1.6 minutes at an oil temperature of 217 C. in the Brabender blending device. Then the silicone was added with the temperature of the mixture being read at 223 C.
initially, and an initial torque of 2010 meter-grams.
After processing at 140 r.p.m. for 1.5 minutes, the torque had risen to 2230 meter^grams. The final temperature of the mixer was 234 C. and resulted in an extrudable mixture capable of forming catheters and other medical devices ~20 which had good thromboresistant characteristics and good tensile strength.
Example 5. To the Brabender Plasticorder of ~xam-ple 1, purged with nitrogen gas and heated to 195 C. was *
added 49 parts by weight of the KRATON G1650 hlock copoly-mer described in Example 2; 21 parts by weight of a poly (ethylene-propylene) copolymer containing 60 to 70 weight * *
percent of ethylene units (EXXON ~istalon 702).
~t Trademark - 16 ~
~his rnixture wa~ mixed in the Brabender device ~t 50 r.p~m. until mixed, after which 30 p~rts by weiyht ~ a dimethylpolysiloxane yum con~aininq 2.9 percent by w~ight of a vinylmethylsiloxane units (Union Carbide W980) , ;_ was added. The rotation of the Brabender device was then ~ increased to 160 r.p.m. with a jacket temperature of 217 C.. After reaction the final material temperature was --~ 236 C. and the inal torque was 1980 meter-grams.
~ The resulting product was molded into a sheet which was strong, flexible, and non-greasy, indicating the crosslinkin~ of the silicone in the formulation.
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- Example 6. To the Brabender Plasticorder mixiny . .
- chamber of Examp:Le 1, using techniques similar to Example 1, was added 24.45 grams of a blend of KRATO~ G1650, Vistalon tsee below) 15- 701 and DQDA2803~in such proportion as to achieve the final - weight percent composition below. Then 15.56 grams of a diphenyl dimethylpolysiloxane with added vinyl groups , ~G.E. 449-358~52) with silane-treated Eumed silica ^~ (Degussa, Inc. Aerosil R-972~ in such proportions as to achieve the composition described ~elow was added. These .- - ingredients were then mixed under a nitrogen cover at high -- shear stress to final conditions of 230 C. at 140 r.p.m.
There was immediately added polypropylene, i.e., Rexene 23M2, which contains a few weight percent ethylene and has a melt flow rate of 2.0 gram~/10 minutes at 230 C.
according to ASTM method D1238-73 and has a density of 0.895 g/cc at 73 F. The final weight percent composition was , * ~ .
35.8 percent KRATON; 9.6 percent Vistalol~ 701i 9.6 percent DQDA2803, 10 percent Rexene 23M2; 15% Aerosil R-972 and 20 percent phenyl methylvinylsiloxane. See Example 2 for ..
': ~ Trade~ark , - 17 -. .
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descriptions of ~K~rroN G1650 and DQD~2803.
Vistalon~701 is an ethylene-propylene copolymer made by EXXON ~hemical Co. to contain approximately 67 weight percent ethylene and 33 weight percent of propylene i units, having a Mooney viscosity of 75 ~260 C~ 8 minutes) and a fairly narrow molecular weight distribution.
Aerosil R972 is a fumed sili¢a whose surface is treated with dimethyldichlorosilane, and is made to have an average primary particle size of 16 nm. , a surface area L0 of 130 square meters per gram (BET method), and a rerac-tive index of 1.45.
The phenylmethylvinyl silicone was 449-358-52 was made by General Electric Company to have approximately 18 million centipoise viscosity (25C.), refractive index 1.5095 (nD at 22 C.), having 20 mole percent diphenylsilo~ane units and 3 mole percent vinylmethylsiloxane Unlts.
The above material was compression molded to make a sheet approximately 15 mils thick, ~hich was transparent, flexible, resilient, and had a higher yield strength and less tackiness, compared to similar materials without silica. The sheet was ~abricated by impulse heat sealing to ma~e a water filled bag, which withstood steam steriliz-ing without becoming sticky or distorting, and without per-menent change in clarity. (~aziness that developed during ~25 steam steriliæation cleared out completely in one day at room conditions. This hazing, commonly called "blush"/ is typicàl of many other materials, especially those materials used to contain drugs and human blood or blood fractions.) Trademark This material is permeable to carbon dioxide at a rate of 102-123 cc--cm/cm-sec-mmHy x 101, which is approximately three to four times higher than currently commercial vinyl blood and blood platelet containers.
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BACKGROUND OF THE INVENTION
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Silicones, particularly polymers and copolymers o dimethylpolysiloxane, are used in numerous medical devices because of the known compatibility of the mater-ials to living ~issue. ~owever, a drawback for the wider usage of silicone in the medical field is ~hat it is expensive, and of relatively low tensile strength when compared with many other ~lexible plastic materials.
Accordingly, there is a need for stronger, less expensive materials than silicone; which at the same time exhibit equivalent tissue compatibility and non-clotting characteristics to silicone materials so that they may be used to make, for example, intravenous catheters de-signed for long-term retention in position of communica-tion with a blood vessel for the administration of parenteral solutions and ~he like.
Grat polymers including silicone materials are known, as described for example in U.S. Patent No.
3~865,897~ In this patent, graft polymers of silicone yum5 with polyethylene, polymethylpentene, polypropylene, and a copolymer of tetra~luorethylene repeating units ~nd ethylene repeating units are disclosed, along with the teaching of how to graft them by placing them under shearing mixing conditions at elevated temperatures.
More details with respect to silicone-poly-ethylene blends are disclosed in the article entitled Sillcone Polyethylene Blends by James R. Falender, et al '~
in Polymer Engineering and Science, Vol. 16, No. 1, January, 1976. However, ~he materials of this type which have been tested have not exhlbited satisfactory melt processability to get a smooth surface, or the desired higher ultimate strength and elastic behavior which would be desired for an intravenous catheter or a blood bag, for example.
Also, it is usually desired for intravenous catheters, in particular, to be radiopaque for purposes o visualization of the catheter on an X-ray fluoroscope or the like. However, silicone catheters which contain enough of a radiopaque filler such as barium sulfate to be strongly radiopaque may be of very low tensile strength.
Polytetrafluoroethylene catheters and catheters made of many other matexials which contain E~ high level of such a radiopaque filler, become unduly stiff.
Accordingly, there is a need for a flexible, plastic material which is relativelv non-clotting and highly tissue compatible, and which can also remain fIex-~0 ible and strong at a high loading of radiopaque iller, forexample on the order of 10 to 50 percent by weight.
~ he formulations of this invention exhibit good compatibility with tissue, reducing the normal irritation of tissue in the presence o a foreign material. Also they have low thrombogenicity, and thus can be used in longer~term contact with blood. Furthermore, the mater-ials of t~is invention can remain relatively flexible and strong, when compared with other medical materials, even when loaded with extraordinarily high amounts of a radiopaque filler such as barium sulfate. Accordingly, tissue-compatible catheters for long-term implantation, and particularly, radiopaque catheters are advantageously made by this present invention.
DESCRIPTION OF THE INVENTION
In accordance with this invention, a flexible composition is provided, being made of a plastic material which comprises (a) from 30 to 50 percent by weight of a block copolymer having thermoplastic rubber characteris-tics and having a central block of a rubbery polyolefin, and terminal blocks of a polystyrene; (b) from 30 to 50 percent by weight of a thermoplastic low crystallinity ethylene polymer such as those selected from the group consisting of poly(ethylene-vinyl acetate) containing rom 0 to 35 percent by weight of vinyl acetate units, or a low - crystallinity polymer of e~hylene containing from 0 to 60 percent by weight of propylene units, and having a molecular weight of at least about 10,000; and (c) from 2 to 30 percent by weight of a cross-linked silicone gum consisting of essen tially of (R2SiO) units, in w~ich R is selected from the group consisting of methyl, phenyl, vinyl, and allyl, at least half of said R groups being methyl, and from 0.5 to 10 mole percent of said R groups being vinyl or allyl prior to crosslinking. The above percentages are calculated with-out regard to filler or other ingredients present apart from 3~3 (a) and (b). Furthermore, we have discovered that the materials of this invention, when containing submicroscopic silica ~iller in conjunction with phenyl-containing sili-cones, are transparent at unexpectedly high levels of silicone and low levels of phanyl-group content.
The above-described materials have been found to be capable of accepting remarkably high loadings of radio-paque filler such as baxi~n sulfate, for example, 10 to 50 percent by weight, while retaining adequate tissue com-patibility, tensile strength, softness, and flexibility,unlike other known medical polymers. Accordingly, a tissue compatible, flexible catheter can be obtained which may be highly radiopaque, for example, I.V. catheters, cen-tral veinous catheters and Foley Catheters. The material may also be used for other medical uses such as blood or platelet bags, where a non-radiopaqu~e material of this in-vention may be used. Particularly, a most desirable intra-venous catheter may be made from the material of this inven-tion, such as a central veinous catheter capable of long-term emplacement for well in excess of a week without ex-cessi~e blood clotting and ~issue trauma.
It is generally preferred for about 20 to 40 percent of barium sulfate or other filler to be present as the radiopaque filler in the plastic material of this in-vention~ However, other radiopaque fillers such as iodine-containing organic compounds, tungsten powder, or bismuth trioxide may also be used as partial or complete substi-tutes for the barium sulfate, in appropriate circumstances.
Ingredient ~a), which is the block copolymer having thermoplastic rubber characteristics, is commer~
cially available in various types and grades, for example, from the Shell Chemical Company under the trademark "KRATON", or from the Phillips Chemical Company under the trademark "SOLPRENE". The rubbery olefin central block may consist of such matexials such polybutadiene, polyisoprene, or poly (ethylene~butylene), the latter being generally pxeferred.
If desired, chain branching units and the like may also be included.
The rigid, usually terminal blocks of ingredient (a) customarily consist of polystyrene, although it is con-templated that derivatives of polystyrene and other e~ui-valent materials can be used as wel:L. Preferably, the Brookield viscosity of ingredient ~a) is 10 to 2000 cps., as a 10 weight percent toluene solution, measured at 25 C.
As ingredient (b), the poLy(ethylene-vinyl ace-tate) preferably contains on the order of 25 to 30 percent by weigh~ of vinyl acetate uni~s, and is a ~hermoplasti polymer. Ingredient (b) serves as flow aid for extrusion of the material of this invention/ and also serves to help provide a more flexible material, even in the presence of the high filler loading~ contemplated in the preferred embodiments. The stiffness of the material of this inven-~5 tion can be controlled to some extent by adjusting thexelative amounts of ingredients (a) and (b), ingredient (b) being of relatively low cost. Also, inyredient ~b) can im-prove the grafting prccess of making these materials.
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Ingredient (b) may also include generally low crystallinity polymers of principally ethylene, preferably having a molecular weight of at least 10,000, for example, low density polyethylene (e.g., a density of about 0.91 to 0.935 g/cc) and copol~mers of ethylene containing up to 60 mole percent of co-polymerized propylene units, in which case the material is known as poly(ethylene-propy-lene).
PreEerably, ingredients (a) and (b), along with any filler that is included, may be initially mixed, for example in a Brabender mixing chamber at a chamber temper~
ature of approximately 190 C.. The chamber is preerably flushed with nitrogen to eliminate oxygen.
Thereafter, ingredient (c), the silicone gum, may be added, and mixed with shearing action at a temperature typically of at least 190 C., although lower temperatures can be used with larger volume mixing equipment, on the order of 150 pounds of ingredients or the like, in which higher shear stresses are obtained in the mixing chamber.
Under these conditions, a crosslinking reaction is belie~ed to ta~e place in the silicone gum, to greatly reduce its migration from the final product plastic material. Also, a grafting reaction may take place under certain circum-stances between the silicone gum and ingredients (a) or (b). These chemical reactions create a strengthened, flexible, elastomeric material having the desired charac-teristics specified above.
The silicone gum, ingredient (c), is preferably present in a concentration of about 5 to 20 percent by weight, without regard to filler or other ingredients than (a) and (b) present, for example, about lO percent by 5 weight. Typically, the silicone gum ma~T have a molecular weight on the order of at least about 70,000 and preferably higher to render the silicone nonextractable from the com-pleted material, and preferably contains a majority o~
dimethylsiloxane tmits so that R as defined above is pre-dominantly meth~l. However, as an alternative, phenylmethyl-siloxane and diphenylsiloxane units may also be included, along with other equivalent siloxane units that do not sig-nificantly chanye the properties of the material, when and as desired. Branched chain siloxane. gums may also be used.
As stated above, in the si.licone gum, from essen-tially 0.5 to 10 mole percent of the R groups should be vinyl or allyl, pre~erably 3 to 6 mole percent, with vinyl groups being localized in blocks or clusters in the mole-cule, in order to impart more completely the desirable properties of silicone to the completed material. These are preferably provided in the form of vinylmethylsiloxane units, although vinyl-containing siloxane units such as divinyl ~iloxane, allylmethylsiloxane, or trivinyl siloxane units may be also used in equivalent quantities.
Alternatively, silicone-bonded reactive groups can be used in combination with or as a substitute for alkenyl groups. For example, silicone gums with Si-H units can crosslink with silicon-bonded vinyl-containing gums, especially in the presence of platinum catalysts. The various other well known crosslinking systems for silicone gums may also be used in appropriate circumstances, such as silicones with attached groups of acetoxy, hydroxy, ethoxy, methoxy and acryloxypropyl siloxane.
The silicone gum provides a surprising degree of softness and flexibility to the finished product, especially at high filler loadings. Surprisingly, silicone gum gener-ally, when mixed in small amounts such as 5 to 30 weight percent with other organic polymers of higher tensile strength, provides a softer material capable of acc~ptiny larger amounts of fillers, and particularly barium sulfate, than the silicone-free organic polymers.
Preferably, 40 to 50 percent by weight each of ingredients (a~ and (b) may be present in the pure plastic material of this invention, while from 8 to 15 percent by weight of ingredient (c) may be present, without regard to filler or other ingredients than (a) and (b) present.
While not wishing to be restricted to any theory of operation of the synthesis of the ~ormulation of this 2Q invention, it is believed that ~he vinyl or allyl groups on the silicone molecule particip~te in a crosslinking or grafting process to provide the finished product claimed in this inventionr Other materials may be added to the formulation of this invention as desired. For example, a reinforcing type submicroscopic silica filler may be utilized, espec-ially when silane-treated for compatibility with the polymer.
However/ it has been generally found that increased amounts of ingredient (c), the silicone gum, are needed in this circumstance because of the strong affini-ty of silane-txeated reinforcing silica filler for the silicone gum.
The incorporation of submicroscopic silica into transparent embodiments of the invention of this application permits the addition of larger amounts of silicones, and silicones at lower refractive index, while retaining transparency.
Other materials such as antioxidants, pigments, and the like may be added as well, but the formulation of this in~ention is preferably free of leachable liquid componen-ts such as oil plasticizers.
~ eat resistance, strength, and stiffness may be increased by adding 5 to 40 percent by weight of highly crystalline polyolefins, such as polypropylene, poly-methylpentene, polyethylene and copolymers of such r without necessarily diminishing the transparency of those composi-tions which are transparent without this addition.
Particularly, when highly crystalline polyolefins are used, it is generally preferred to use from 5 to 25 percent by weight of such a material, for example, poly-propylene, the percentage being based on the entire weightof the composition.
When submicroscopic or fume silica is used, it is generally preferred that approximately from 10 to 30 percent by weight be present, based upon the weight of the entire composition, In this preferred composition at least 10 mole percent of the R groups present in the crosslinkable silicone gum are phenyl groups, It has been particularly found that when clear compositions in accordance with this invention are desired to be used, the use of phenyl-containing silicone compositions tend to improve the clarity. It has been found that when fume silica is used as a filler, equal clarity in a compo-sition can be achieved while using a silicone composition having a lower phenyl content, which is generally a less expensive material.
In the drawings, ~igure 1 is a perspective view of a central veinous catheter made in accordance with this invention.
Figure 2 is a perspective view of the central veinous catheter of this invention shown emplaced in a patient.
Referring to the drawings, the central veinous catheter 10 comprises a flexible, tubular shaft 12 which may be made of the elastomeric material of this invention, and a conventional hub 13 at one end thereof, which may be made of any desired plastic material. Hub 13 is pro-vidPd as a connector member ~or other parts, and may also be used as a suturing site to prevent withdrawing of the catheters, as is conventionally known.
As shown in Figure 2, the catheter of this in-2Q vention may be inserted into a vein of a patient by being pas~ed through a relatlvely short introducer catheter 14 which, in turn, carries at its end a hub 16. A connection from a parenteral solution source or the like may then communicate thorugh the bore of hub 16 to provide ~luid connection through hub 13 and catheter 12.
The above catheter system may be similar to the CENTRASIL T-~- silicone elastomer central veinous catheter which is currently sold by the Vicra Division o Travenol Laboratories, Inc., Dallas, Texas, with the material of ~L3~
catheter shaft 12 being m~e in accordance with this in-vention for yood flexibility, softness, kink resistance, thrombo-resistance, high strength, and low friction, in conjunction with good visibility by X-ray.
`'~ Catheter guard 18 is placed near the front end ~, ,, ~ o~ introducer catheter 14 after the emplacement of central : veinous catheter 12, with the introducer catheter 14 beiny withdrawn out of the central vein, but its tip is still allowed to remain in subcutaneous position in the ~l0 final emplacement. This reduces the possibility of irri-tation to the vein.
~- The exarnples below are providèd for illustrative purposes only, and are not intended to limit the scope of the invention of this application, which is as defined in the claims below.
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Example 1. To a Brabender ~lasticorder, Model MV100, with an attached mixing/measuring head, purged with nitrogen gas and heated to 195 C., was added (a) 13.5 grams of a block copolymer (KR~TON G1662) having thermo-'0 plastic rubber characteristics, with a central block of - ethylene and butylene copolymer units in generally equal molar proportions, and terminal blocks of polystyrene, in which the ethylene-butylene portion of the copolymer comprises about 70 percent by weight of the copolymer mole-cule, and the material has a Brookfield viscosity at 25 C.
of 20 cps.~ using a 10 weight pexcent solution in toluene, and containing from 0.03 to 0.07 percent by weight of A0330 antioxidant (sold by Ethyl Corporation); (b3 13.5 grams of * Trademark ~, .
poly(ethylene-virlyl ac~tate) having a vlnyl acetate content of 28 percent and a melt index of 3.5, as tested by ASTM
test D-1238-73, condition E, (Ultrathene UE 634-00, sold by U.S. Industries); and 12 ~ 8 grams of finely powdered barium sulfate (Blanc Fixe XR [Barium Sulfate XR] sold by the Ore and Chemical Co.).
This mixture was mixed in the Brabender device fox two minutes under a nitrogen atmosphere. Following this, 3.0 grams of (c) a dimethylpolysiloxane gum contain-. !0 ing approximately 5 weight percent of methylvinylsiloxaneunits (Union Carbide Y8203 or Rhodia Co. RC356) was added.
The Brabender fixed cam blade rotor type mixing chamber was brought to a ~inal temperature of 225Co while exert-ing maximum torque in the shearing mixing. The reaction 5 time to maximum torque was 2.7 minutes, followed by a mixing time of 3.3 minutes. The initial torque was 2150 meter-grams, and the final torque 2245 meter-grams. The final temperature of the material processed was 238 C. with the Brabender - mixing rotors rotating at 190 r.p.m.
~0 The above pxocess was repeated on fifteen separ-ate occasions to provide sufficient material or extru-sion of a tube. Therea~ter, a tube having a bore diameter of approximately 0.035 inch and an outer diameter of 0.065 inch was extruded out of the material. The extruded tubing ~25 was cut into 21 inch lengths, and hubs were attached to the tubing as illustrated in the drawing and described above, for providing central veinous catheters.
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* Trademark The resultin-3 central veinous catheters exhibit excellent tissue compatibility, as illustrated by super-ior nonthrombogenic charac-teristics of the type generally exhibitecl by silicone rubber. The catheters were flexible and highly radiopaque, while retaining improved tensile strength, lower friction, and were easier to maintain free of attracted dust and the like, compared with pure silicone catheters having similar or lesser amounts of barium sul-fate or tungsten as a filler.
LO Example 2. To the previous Brabender mixin~ de-vice, purged with nitrogen gas, and heated to 195 C. was :: *
added (a) 40 parts by weight of a block copolymer (KRATON
Gl650) having thermoplastic rubber characteristics with a central block of ethylene and butylene copolymer units in L5 equal molar portions, and terminal blocks of polystyrene, the material having a Brookfield viscosity of 1,500 cps.
at 20 weight percent in toluene at 77 F.; 40 parts by weight o~ (b) a poly(ethylene-vinyl acetate) thermoplastic having 28 percent by weight of vinyl acetate units and a melt index of 1.5 (Union Caxbide DQDA2803). These materials were mixed in the Brabender mixing chamber in pelletized - form under nitrogen at 140 r.p.m. No filler was usedO
Thereafter, 20 parts by weight of (c) a soft sili-cone gum (General Electric 449-336-15) having a viscosity ~5 of 55 million centipois~ at 25 C. and containing 4 mole percent vinylmethylsiloxane units, 20 mole percent diphenyl siloxane units, and essentially the balance being dimethyl-siloxane units, were added to provide a 40 gram batch in * Trademark ,, .
~ 3 ~
khe compoundillg machine. Tl-e machine was operated for four rninutes under nitrogen at 140 r.p.m. in a mixing and purge cycle, and therea~ter for four minutes for completion of the grafting process~ The initial torque was 1720 metex-grams, and a final torque of 2480 meter-grams. The initial oil temperature of the compounding machine was 208 C. and - the final temperature of the material processor was 239 C.
Thereafter, the material was allowed to cool for 1 1/2 minutes under nitrogen at 20 r.p.m., removed and ex-L0 truded as tubing which ~-as strong, soft, kink-resistant, heat sealable, having good thromboresistant characteristics and improved transparency for viewing blood.
The refractive index of the silicone material is selected to essentially match the reEractive index o~ the other ingredients for improved clarity.
Addition of 10 weight percent polypropylene (Rexene 23M2, made by Rexene Polyolefins Co.) having a melt flow rate of 2.0 and a density of 0.895 g/cc provides a transparent material also capable of steam sterilization.
It has high gas permeability, which is advan~ageous for storing blood components, especially platelets.
Example 3. The formulation of Example 1 was prepared; enough barium sulfate radiopaque filler was added to provide a formulation in which the amount of barium sul-fate present was 40 percent by weight of the amount ofplastic material. The resulting product still exhibited acceptable flexibility, kink-resistance, strength, and thrombo-resistance, although showing slightly more trauma to the inside blood vessel wall~
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Exam~le 4. The process o~ Example 2 was repeated, utilizing 45 percent by weight of khe ICRATON G1650 material for ingredient (a); 45 pexcent o the same ethylene vinyl acetate copolymer ~or ingredient (b), and using no filler.
After initial mixing under a nitrogen purge in the Braben-der blending device,l0 percent by weight of Union Carbide W980 silicone ~um was added, being a random copolymer gum of dimethylsiloxane units and 3.5 weight percent methyl-vinylsiloxane units, and end blocked with trimethylsiloxane Q0 units.
The mixture was fluxed at 140 r.p.m. under nitro-gen for 1.6 minutes at an oil temperature of 217 C. in the Brabender blending device. Then the silicone was added with the temperature of the mixture being read at 223 C.
initially, and an initial torque of 2010 meter-grams.
After processing at 140 r.p.m. for 1.5 minutes, the torque had risen to 2230 meter^grams. The final temperature of the mixer was 234 C. and resulted in an extrudable mixture capable of forming catheters and other medical devices ~20 which had good thromboresistant characteristics and good tensile strength.
Example 5. To the Brabender Plasticorder of ~xam-ple 1, purged with nitrogen gas and heated to 195 C. was *
added 49 parts by weight of the KRATON G1650 hlock copoly-mer described in Example 2; 21 parts by weight of a poly (ethylene-propylene) copolymer containing 60 to 70 weight * *
percent of ethylene units (EXXON ~istalon 702).
~t Trademark - 16 ~
~his rnixture wa~ mixed in the Brabender device ~t 50 r.p~m. until mixed, after which 30 p~rts by weiyht ~ a dimethylpolysiloxane yum con~aininq 2.9 percent by w~ight of a vinylmethylsiloxane units (Union Carbide W980) , ;_ was added. The rotation of the Brabender device was then ~ increased to 160 r.p.m. with a jacket temperature of 217 C.. After reaction the final material temperature was --~ 236 C. and the inal torque was 1980 meter-grams.
~ The resulting product was molded into a sheet which was strong, flexible, and non-greasy, indicating the crosslinkin~ of the silicone in the formulation.
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- Example 6. To the Brabender Plasticorder mixiny . .
- chamber of Examp:Le 1, using techniques similar to Example 1, was added 24.45 grams of a blend of KRATO~ G1650, Vistalon tsee below) 15- 701 and DQDA2803~in such proportion as to achieve the final - weight percent composition below. Then 15.56 grams of a diphenyl dimethylpolysiloxane with added vinyl groups , ~G.E. 449-358~52) with silane-treated Eumed silica ^~ (Degussa, Inc. Aerosil R-972~ in such proportions as to achieve the composition described ~elow was added. These .- - ingredients were then mixed under a nitrogen cover at high -- shear stress to final conditions of 230 C. at 140 r.p.m.
There was immediately added polypropylene, i.e., Rexene 23M2, which contains a few weight percent ethylene and has a melt flow rate of 2.0 gram~/10 minutes at 230 C.
according to ASTM method D1238-73 and has a density of 0.895 g/cc at 73 F. The final weight percent composition was , * ~ .
35.8 percent KRATON; 9.6 percent Vistalol~ 701i 9.6 percent DQDA2803, 10 percent Rexene 23M2; 15% Aerosil R-972 and 20 percent phenyl methylvinylsiloxane. See Example 2 for ..
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descriptions of ~K~rroN G1650 and DQD~2803.
Vistalon~701 is an ethylene-propylene copolymer made by EXXON ~hemical Co. to contain approximately 67 weight percent ethylene and 33 weight percent of propylene i units, having a Mooney viscosity of 75 ~260 C~ 8 minutes) and a fairly narrow molecular weight distribution.
Aerosil R972 is a fumed sili¢a whose surface is treated with dimethyldichlorosilane, and is made to have an average primary particle size of 16 nm. , a surface area L0 of 130 square meters per gram (BET method), and a rerac-tive index of 1.45.
The phenylmethylvinyl silicone was 449-358-52 was made by General Electric Company to have approximately 18 million centipoise viscosity (25C.), refractive index 1.5095 (nD at 22 C.), having 20 mole percent diphenylsilo~ane units and 3 mole percent vinylmethylsiloxane Unlts.
The above material was compression molded to make a sheet approximately 15 mils thick, ~hich was transparent, flexible, resilient, and had a higher yield strength and less tackiness, compared to similar materials without silica. The sheet was ~abricated by impulse heat sealing to ma~e a water filled bag, which withstood steam steriliz-ing without becoming sticky or distorting, and without per-menent change in clarity. (~aziness that developed during ~25 steam steriliæation cleared out completely in one day at room conditions. This hazing, commonly called "blush"/ is typicàl of many other materials, especially those materials used to contain drugs and human blood or blood fractions.) Trademark This material is permeable to carbon dioxide at a rate of 102-123 cc--cm/cm-sec-mmHy x 101, which is approximately three to four times higher than currently commercial vinyl blood and blood platelet containers.
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Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A flexible composition made of a plastic material which comprises (a) from 30 to 50 percent by weight of a block copolymer having thermoplastic rubber characteristic and having a central block of a rubbery polyolefin and terminal blocks of a polystyrene; (b) from 30 to 50 percent by weight of a thermoplastic low crystallinity ethylene polymer selected from the group consisting of a poly(ethylene-vinyl acetate) containing from 10 to 35 percent by weight of vinyl acetate units and low-crystallinity polymers of ethylene containing from 0 to 60 percent by weight of propylene units, and having a molecular weight of at least about 10,000; and (c) from 2 to 30 percent by weight of a chemically reactive grafted silicone gum consisting essentially of (R2SiO) units, in which R is selected from the group consisting of methyl, phenyl, allyl, and vinyl, at least half of said R groups being methyl, and from 0.5 to 10 mole percent of said R
groups being allyl or vinyl, prior to their chemical reaction,
groups being allyl or vinyl, prior to their chemical reaction,
2. The composition of claim 1 which contains from 10 to 50 percent by weight of a radiopaque filler.
3. The composition of claim 2 in which said radio-paque filler is barium sulfate.
4. The composition of claim 1 in which said rubbery polyolefin is a copolymer of generally equal proportions of ethylene and butylene units.
5. The composition of claim 1 in which some 40 to 50 percent by weight of each of ingredients (a) and (b) are present and from 5 to 20 percent by weight of ingredient (c) is present, said percentages being based on the composition without filler and other additives.
6. The flexible composition of claim 1 in which said siloxane units are free of phenyl groups.
7. A catheter made of the composition of claim 2.
8. A catheter of claim 7 which is an intravenous catheter.
9. The catheter of claim 7 in which said radiopaque filler is barium sulfate.
10. The catheter of claim 9 in which said rubbery olefin is a copolymer of generally equal proportions of ethylene and butylene units.
11. The catheter of claim 10 in which some 40 to 50 percent by weight of each of ingredients (a) and (b) are present and from 5 to 20 percent of ingredient (c) is present, said percentages being based on the composition without filler and other additives.
12. The catheter of claim 11 in which said siloxane units are free of phenyl groups.
13. The composition of claim 1 which also includes from 5 to 40 percent by weight of a highly crystalline poly-olefin for improved heat-resistant strength and stiffness.
14. The composition of claim 13 in which said highly crystalline polyolefin is polypropylene which is present in the amount of 5 to 25 percent by weight.
15. The composition of claim 14 in which from 10 to 30 percent by weight of submicroscopic silica is present, based on the weight of the entire composition.
16. The composition of claim 15 in which, in said cross-linkable silica gum which is present, at least 10 mole percent of said R groups are phenyl.
17. The flexible composition which is formed when the chemically reactive silicone gum is cross-linked or grafted in the composition of claim 1.
18. The flexible composition of claim 1 in which ingredient (b) is a low-crystallinity polymer of ethylene containing 30 to 40 weight percent of propylene units.
19. The flexible composition of claim 1 in which ingredient (b) contains at least ten percent by weigh-t of vinyl acetate units.
20. The flexible composition of claim 1 which is essentially free of leachable liquid components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US888,253 | 1978-03-17 | ||
| US05/888,253 US4196731A (en) | 1978-03-17 | 1978-03-17 | Silicone-containing thermoplastic polymers for medical uses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134088A true CA1134088A (en) | 1982-10-19 |
Family
ID=25392857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA321,982A Expired CA1134088A (en) | 1978-03-17 | 1979-02-21 | Silicone-containing thermoplastic polymers for medical uses |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4196731A (en) |
| JP (1) | JPS54130656A (en) |
| CA (1) | CA1134088A (en) |
| DE (1) | DE2909369A1 (en) |
| GB (1) | GB2016482B (en) |
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| US4861830A (en) * | 1980-02-29 | 1989-08-29 | Th. Goldschmidt Ag | Polymer systems suitable for blood-contacting surfaces of a biomedical device, and methods for forming |
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| CN108329440B (en) * | 2018-01-24 | 2020-08-25 | 中国科学院长春应用化学研究所 | Low drug adsorption TPS and preparation method and application thereof |
| CN108587039A (en) * | 2018-05-31 | 2018-09-28 | 安徽电信器材贸易工业有限责任公司 | A kind of corrosion resistant submarine optical fiber cable sheath material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT563327A (en) * | 1955-12-05 | |||
| FR1505631A (en) * | 1966-11-16 | 1967-12-15 | Catheter development | |
| GB1257304A (en) * | 1968-03-29 | 1971-12-15 | ||
| US3508551A (en) * | 1968-06-20 | 1970-04-28 | Parke Davis & Co | Dressings and production thereof |
| GB1430077A (en) * | 1972-07-31 | 1976-03-31 | Ici Ltd | Silicone elastomers |
| US3829903A (en) * | 1972-12-11 | 1974-08-20 | Dow Corning | Method of inhibiting blood clot on silicone rubber medical devices |
| US3865897A (en) * | 1973-08-03 | 1975-02-11 | Dow Corning | Method of blending polyolefins and polydiorganosiloxane gums and blends thereof |
| DE2848854A1 (en) * | 1977-11-21 | 1979-05-23 | Baxter Travenol Lab | CATHETERS, ESPECIALLY BALLOON CATHETERS, AND PLASTIC DIMENSIONS FOR ITS PRODUCTION |
-
1978
- 1978-03-17 US US05/888,253 patent/US4196731A/en not_active Expired - Lifetime
-
1979
- 1979-02-21 CA CA321,982A patent/CA1134088A/en not_active Expired
- 1979-03-09 DE DE19792909369 patent/DE2909369A1/en not_active Ceased
- 1979-03-16 GB GB7911261A patent/GB2016482B/en not_active Expired
- 1979-03-16 JP JP3099279A patent/JPS54130656A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB2016482B (en) | 1982-08-18 |
| DE2909369A1 (en) | 1979-12-20 |
| JPS6142745B2 (en) | 1986-09-24 |
| GB2016482A (en) | 1979-09-26 |
| JPS54130656A (en) | 1979-10-11 |
| US4196731A (en) | 1980-04-08 |
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