WO1992019288A1 - Catheter dont la surface exposee est pourvue d'un enrobage - Google Patents

Catheter dont la surface exposee est pourvue d'un enrobage Download PDF

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Publication number
WO1992019288A1
WO1992019288A1 PCT/DK1992/000132 DK9200132W WO9219288A1 WO 1992019288 A1 WO1992019288 A1 WO 1992019288A1 DK 9200132 W DK9200132 W DK 9200132W WO 9219288 A1 WO9219288 A1 WO 9219288A1
Authority
WO
WIPO (PCT)
Prior art keywords
catheter
poly
balloon
hydroxy
coating
Prior art date
Application number
PCT/DK1992/000132
Other languages
English (en)
Inventor
Denis Keith Gilding
Simon Ashley Dixon
Jeremy Paul Watson
Ian Michael Harrison
Original Assignee
Pharma-Plast International A/S
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 Pharma-Plast International A/S filed Critical Pharma-Plast International A/S
Publication of WO1992019288A1 publication Critical patent/WO1992019288A1/fr

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Classifications

    • 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
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a novel compound being a poly(N-(mono hydroxy)propyl methacrylamide) and its use for preparing a coating on the surface of a tubular device (including a Foley balloon catheter for urinary drainage purposes) for supplying fluid (gas or liquid) to, or removing fluid from, the body of a patient.
  • a tubular device including a Foley balloon catheter for urinary drainage purposes
  • fluid gas or liquid
  • tubular devices on the surface of which the compound of the invention may be applied include catheters (e.g. cardiovascular catheters and radiological catheters), and anaesthesia tubes (e.g. endotrachial tubes).
  • catheters e.g. cardiovascular catheters and radiological catheters
  • anaesthesia tubes e.g. endotrachial tubes
  • the present invention relates to a Foley balloon catheter for urinary drainage purposes and a method of producing the catheter.
  • a Foley balloon catheter which generally comprises an elongate extrusion subdivided longitudinally into a main (or drainage) lumen and a secondary (or inflation) lumen.
  • the main lumen communicates with a drainage aperture in the wall of the extrusion adjacent the insertion end of the catheter whereby urine from the bladder passes through the drainage aperture along the main lumen and drains from the outlet end of the catheter.
  • the catheter further comprises an elastomeric sleeve or balloon which (in use of the catheter) is also located in the bladder and which is inflated by fluid pressure passed along the inflation lumen.
  • the catheter (with balloon deflated) is inserted along the urethra! passageway so that the drainage aperture and balloon locate ind the bladder.
  • the balloon is then inflated so that the catheter is prevented from being withdrawn from the patient.
  • the inflation of the balloon is maintained by a valve associated with the inflation lumen.
  • the catheter may be required to be maintained in the body for several months, after which the fluid pressure is released and the catheter is withdrawn.
  • the catheter have (over at least that part of its length which is inserted in the body) a surface which has a low-coefficient of friction when in contact with aqueous body fluids.
  • the wetted surface should feel "slippery".
  • Such a surface also minimizes rubbing between the catheter and the urethra! passageway during residence of the catheter in the body and therefore minimizes discomfort to the patient.
  • the hydrophilic coating further reduces the tendency to become encrusted, and reduces the incidence of infection.
  • the catheter comprising an elongate body sub-divided into a drainage lumen and an inflation lumen, a balloon provided towards said insertion end of the catheter and being adapted for inflation by fluid pressure sup plied along the inflation lumen, and a drainage aperture provided towards said insertion end of the catheter for communication with said drainage lumen to drain urine to said outlet, wherein at least over a portion of its length extending from the insertion end to a position beyond the balloon, the exposed surfaces of the body and of the balloon are of a polyurethane and over said length the body and the balloon are provided with a coating of a poly(N-(mono hydroxy)propyl methacrylamide) bonded to said polyurethane surface by residues of a di or higher functionality isocyanate compound.
  • a method of producing a Foley balloon catheter as defined in the preceding paragraph wherein said exposed surface is treated with a di or higher functionality isocyanate compound and a poly (N- (mono hydroxy)propyl methacrylamide) whereby the latter is bonded by isocyanate residues to provide a coating on said surface.
  • the poly(N-(mono hydroxy ) propy 1 methacrylamide) is poly (N- (2-hydroxy)propyl methacrylamide), although other isomers in which the hydroxy group is at a different position on the propyl chain may be used.
  • the invention will be specifically described with respect to poly (N-(2-hydroxy)-propyl methacrylamide) although the following description is applicable mutatis mutandis to the other isomers.
  • HPMA poly (N-(2-hydroxy)propyl methacrylamide)
  • HPMA poly (N-(2-hydroxy)propyl methacrylamide)
  • the poly (N-(2-hydroxy)propyl methacrylamide) provides a coating which is a "glassy material” when dry and a hydrogel when wetted with aqueous body fluids.
  • the HPMA Upon wetting, the HPMA provides the necessary low friction coating which facilitates insertion and withdrawal of the catheter and prevents damage from "rubbing" between the catheter and the body of the patient, e.g. the urethra! passageway.
  • the HPMA provides several advantages.
  • the wetted HPMA provides low friction for insertion and low mechanical trauma to biological tissue. Additional advantages are better blood, urine and tissue compatibility as well as reduction of infection rates.
  • the HPMA has a molecular weight (M n ) of at least 20,000 daltons as measured by GPC using polystyrene standard calibration.
  • M n molecular weight
  • the HPMA is a homopolymer although comonomers can be included, preferably in an amount less than 10% by mole, more preferably less than 2% by mole.
  • a preferred such comonomer is methacrylic acid.
  • the body of the catheter is of polyurethane, e.g. Estane (Goodrich), Pellethane (Dow) or Elastolan (BASF).
  • the body is of a different material which is coated with a polyurethane.
  • the balloon is of a natural or synthetic natural rubber, eg. cis-polyisoprene and is provided with a surface coating of a polyurethane.
  • This surface coating is preferably of soft polyurethane having a Shore A hardness of less than 80, preferably less than 65. Examples of such polyurethanes are Eurothane 2002 and Eurothane HPU 1010 (Beam Tech Ltd). The use of such a soft polyurethane allows the balloon to expand without cracking.
  • the polyurethane may be applied by means of a dipping process from a solution in DMF (or DMAC, DMS0, or NMP) with THF or Butan-2-one at a concentration of 8%-25% w/v, preferably 10%-15% w/v. After this dipping process, the catheter is dried, e.g. for 20 minutes at 60-70°C.
  • the HPMA is bonded to the polyurethane surface of the catheter tube and balloon by means of residues of a di or higher functionality isocyanate compound.
  • This isocyanate compound may be aliphatic, aromatic or alicyclic. Examples of suitable isocyanates are aliphatic diisocyanates having 3 to 10 carbon atoms, more preferably 5 to 7 carbon atoms.
  • a preferred aliphatic diisocyanate is hexamethylene diisocyanate (HDI). Of the aromatic isocyanates which may be used, the preferred compound is pure MDI or HMDI. The bonding of the HPMA coating to a polyurethane surface is illustrated somewhat schematically below.
  • the first of the above illustrations shows the isocyanate residue being bonded to an oxygen atom of the HPMA, it is also possible it is bonded to a nitrogen atom, as shown by the second of the above illustrations, and it is also possible it is bonded to a carbon atom.
  • the HPMA coating may be applied to the polyurethane surfaces of the catheter body and balloon in a number of ways, examples of which are given below.
  • a solution of the isocyanate (e.g. MDI) and HPMA is formulated in a suitable solvent.
  • concentration of the diisocyanate in the solution will be in the range 0.5-5% whereas the concentration of the HPMA will generally be 1-5%.
  • Suitable solvents include dimethyl formamide (DMF) as well as mixtures of DMF with lower boiling solvents e.g. tetrahydrofuran or methyl ethyl ketone.
  • DMAC, DMSO and NMP may also be used.
  • That length of the catheter which is to be provided with the HPMA coating is dipped into the above described solution, typically for a time of less than 10 seconds. After this dipping process, the catheter is "dried" to leave the surface coating of HPMA bonded to the polyurethane by isocyanate compound residues. Typically the drying condition includes IR drying (e.g. 4-8 min. at 65-70°C) followed by drying (in a fan oven) for several hours at 50-70°C, (e.g. 3-8 hrs at 60°C).
  • the length of the catheter is initially dipped into a solution of the isocyanate (the isocyanate solution) so that isocyanate compound residues become bonded to the polyurethane, followed by dipping into a solution af the HPMA (the HPMA solution), preferably containing a catalyst for forming polyurethanes.
  • the solvent for the isocyanate solution is preferably a halocarbon, preferably one containing chlorine and/or fluorine. Preferred examples of such solvents are low boiling liquids such as methylene chloride, chloroform etc.
  • the concentration of the isocyanate is preferably 1-5%.
  • the dipping time of the catheter in the isocyanate solution is preferably less than 10 seconds.
  • the catheter is removed from the solution and the solvent is allowed to evaporate in air prior to the catheter being dipped in the HPMA solution containing a polyurethane formation catalyst.
  • a suitable concentration range for the HPMA is 0.5-5% and the preferred solvent is a mixture of DMF (50-75%) and THF (50-25%). Other solvents which can be used include DMAC, DMSO, and NMP.
  • the polyurethane formation catalyst is preferably used in an amount of 1 part of catalyst per 500-10,000 parts of HPMA.
  • the catalyst may for example be stannous octoate, stannous chloride, diethyl zinc, diphenyl zinc, and other common organometal 1 ic catalysts used in polyurethane formation reactions. This dipping process is preferably effected for less than 10 seconds.
  • the catheter Upon removal of the catheter from the HPMA solution, the catheter is dried preferably at a temperature of 65-70°C for 8-12 min. Finally the catheter is washed with water and dried in warm air.
  • At least a portion of.the length of the catheter has a surface of HPMA covalently bonded to the polyurethane.
  • This covalent bonding ensures that the HPMA is firmly bonded to the catheter surface and so can repeatedly be made hydrophilic.
  • the HPMA becomes a hydrogel and can expand with the balloon.
  • the polyurethane coating on the outer surface of the balloon allows high expansion of the balloon. Furthermore, the polyurethane has a degree of hydrophilicity and provides a "transition" between the hydrophobic polyisoprene of the balloon and the hydrophilic HPMA. This prevents delamination of the HPMA coating from the balloon.
  • the HPMA coating may include an anti-microbial agent or a drug for delivery to the body of the patient, e.g. copper or silver compounds, chlorohexidi ne or other antiseptic, or an antibiotic. These compounds may be incorporated either in the HPMA or soft polyurethane layers and may either be released or maintained by covalent linkage to the catheter surface.
  • Fig. 1 illustrates the catheter
  • Fig 2 is a detail of Fig 1;
  • Fig. 3 illustrates the sleeve for forming the balloon in the catheter of Fig. 1.
  • the illustrated catheter 1 comprises an elongate polyurethane extrusion 2 internally formed with a primary (or drainage) lumen 3 and a secondary (or inflation) lumen 4 (see also Fig. 2) which extend generally parallel to each other along the extrusion 2.
  • the primary lumen 2 provides communication between a drainage outlet 5 provided at the outlet end (the right hand end as viewed in Fig. 1) of the catheter and a drainage aperture 6 in the wall of the extrusion 2 towards the opposite insertion end of the catheter.
  • the inflation lumen 4 provides communication between a valve arrangement 7 at the outlet end of the catheter and a small aperture 8 provided a short distance from drainage aperture 6 in the direction of the outlet 5.
  • a sleeve or balloon 9 of a synthetic elastomer (e.g. polyisoprene) is bonded by the end regions of its inner surface to the outer surface of the extrusion 2 so as to be inflatable by fluid pressure supplied along inflation lumen 4.
  • Fig. 3 illustrates (to a much enlarged scale) the sleeve 9 before its location on the extrusion 2.
  • the sleeve 9 is moulded slightly under size for location on the extrusion 2 and the end regions of its inner surfaces taper inwardly as shown (e.g. at an angle of about 5° relative to the outer surface of the sleeve). This ensures that, when the sleeve 9 is stretched into position on the extrusion 2, the outer surfaces of the end regions of sleeve 9 provide a smooth transition between the outer surface of extrusion 2 and the main length of the sleeve 9 (see Fig. 1). This facilitates insertion and withdrawal of the catheter.
  • the inner surface of sleeve 9 has a plurality of axially spaced circumferential ribs 10.
  • the purpose of the ribs 10 is to ensure minimum contact between the extrusion 2 and the inner surface of sleeve 10 (during storage of the catheters). This prevents the sleeve 10 sticking to the extrusion 2.
  • the inner surface of the sleeve 9 Prior to being located on the extrusion 2, at least the inner surface of the sleeve 9 is treated with a halogen solution to render this surface receptive to adhesive.
  • the adhesive may be a polyurethane adhesive.
  • the treatment with the halogen solution prevents the inner surface of the sleeve sticking to the outer surface of the polyurethane body during storage of the catheter.
  • the catheter is inserted along the urethra! passageway of a patient so that the drainage aperture 6 and the sleeve 9 locate in the bladder.
  • a suitable source of fluid pressure is then applied to valve 7 so as to cause expansion of the sleeve 9 into the form of a balloon which prevents withdrawal of the catheter.
  • the bladder is drained by virtue of urine passing into aperture 6, along lumen 3, and through the outlet 5.
  • the fluid pressure inflating the balloon 10 is released so that the balloon deflates and the catheter may be withdrawn.
  • the catheter is generally conventional.
  • a portion of the length of the catheter as depicted by the distance "a" in Fig. 1 is provided with a surface treatment of HPMA applied in the manner described above.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Un composé chimique à base de poly(N-(mono hydroxy)propyle méthacrylamide) est utilisé pour préparer une matière d'enrobage devant être appliquée sur la surface d'un dispositif tubulaire, tel qu'un cathéter destiné à des drainages urinaires.
PCT/DK1992/000132 1991-04-25 1992-04-24 Catheter dont la surface exposee est pourvue d'un enrobage WO1992019288A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9109069.6 1991-04-25
GB919109069A GB9109069D0 (en) 1991-04-25 1991-04-25 Catheter

Publications (1)

Publication Number Publication Date
WO1992019288A1 true WO1992019288A1 (fr) 1992-11-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DK1992/000132 WO1992019288A1 (fr) 1991-04-25 1992-04-24 Catheter dont la surface exposee est pourvue d'un enrobage

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AU (1) AU1741492A (fr)
GB (1) GB9109069D0 (fr)
WO (1) WO1992019288A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156852A1 (fr) * 2004-07-07 2010-02-24 Coloplast A/S Preparation de revêtements hydrophiles utilisant un composé 1,3-dioxolane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931111A (en) * 1972-02-29 1976-01-06 Ceskoslovenska Akadamie Ved Soluble hydrophilic polymers and process for processing the same
EP0214721A1 (fr) * 1985-07-05 1987-03-18 Franklin Medical Limited Cathéters à ballonnet
EP0370657A2 (fr) * 1988-11-23 1990-05-30 Minnesota Mining And Manufacturing Company Revêtements en polymère cristallisé non réticulé
EP0379156A2 (fr) * 1989-01-17 1990-07-25 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Revêtements hydrophiles lubrifiés améliorés
EP0166998B1 (fr) * 1984-06-04 1991-05-08 TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION Instrument médical et son procédé de fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931111A (en) * 1972-02-29 1976-01-06 Ceskoslovenska Akadamie Ved Soluble hydrophilic polymers and process for processing the same
EP0166998B1 (fr) * 1984-06-04 1991-05-08 TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION Instrument médical et son procédé de fabrication
EP0214721A1 (fr) * 1985-07-05 1987-03-18 Franklin Medical Limited Cathéters à ballonnet
EP0370657A2 (fr) * 1988-11-23 1990-05-30 Minnesota Mining And Manufacturing Company Revêtements en polymère cristallisé non réticulé
EP0379156A2 (fr) * 1989-01-17 1990-07-25 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Revêtements hydrophiles lubrifiés améliorés

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156852A1 (fr) * 2004-07-07 2010-02-24 Coloplast A/S Preparation de revêtements hydrophiles utilisant un composé 1,3-dioxolane
US7722915B2 (en) 2004-07-07 2010-05-25 Coloplast A/S Preparation of hydrophillic coatings utilizing a 1,3-dioxolane compound

Also Published As

Publication number Publication date
GB9109069D0 (en) 1991-06-12
AU1741492A (en) 1992-12-21

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