WO1992019290A1 - Tubular device with hydrophilic surface - Google Patents

Tubular device with hydrophilic surface Download PDF

Info

Publication number
WO1992019290A1
WO1992019290A1 PCT/EP1992/000919 EP9200919W WO9219290A1 WO 1992019290 A1 WO1992019290 A1 WO 1992019290A1 EP 9200919 W EP9200919 W EP 9200919W WO 9219290 A1 WO9219290 A1 WO 9219290A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
catheter
poly
hpma
tubular device
Prior art date
Application number
PCT/EP1992/000919
Other languages
French (fr)
Inventor
Ian Philip Middleton
Ian Michael Harrison
Jeremy P. Watson
Dennis Keith Gilding
Original Assignee
Polymedica Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polymedica Industries, Inc. filed Critical Polymedica Industries, Inc.
Publication of WO1992019290A1 publication Critical patent/WO1992019290A1/en

Links

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

Definitions

  • the present invention relates to a tubular device (other than a Foley balloon catheter for urine drainage purposes; for supplying fluid (gas or liquid) to, or removing fluid from, the body of a patient.
  • tubular devices with which the present invention is concerned include catheters (eg. cardiovascular catheters and radiological catheters), and anaesthesia tubes (eg. endotrachial tubes).
  • catheters eg. cardiovascular catheters and radiological catheters
  • anaesthesia tubes eg. endotrachial tubes
  • catheters e.g. endotrachial tubes
  • 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 minimises rubbing between the catheter and the body of the patient during residence of the catheter in the body and therefore minimises discomfort to the patient.
  • a catheter other than a Foley balloon catheter comprising an elongate tubular body having one end for insertion in the body of a patient wherein at least over a portion of its length extending from the insertion end the exposed surface of the body is of a polyurethane and over said length the body is provided with a coating of 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 catheter as defined in the preceding paragraph comprising treating said exposed surface with a di or higher functionality isocyanate compound and with poly(X-(mono hydroxy)propyl methacrylamide) so that the latter is bonded to said surface by residues of the di or higher functionality isocyanate compound to form a coating on the surface.
  • the poly(N-(mono hydroxy)propyl methacrylamide) is poly(N-(2-hydroxy)propyl methacrylamide), although other isomers in which the hydroxy group is at a different position or. the prcpyl chain may be used.
  • the invention will be specifically described with respect to poly(X-(2-hydroxy)propyl methacrylamide ) although the following description is applicable mutatis mutandis to the other isomers.
  • HPMA poly(N-(2-hydroxy)propyl methacrylamide)
  • the poly(N-(2-hydroxy)propyl methacrylamide) (hereinafter referred to simply as HPMA) provides a coating which is a "glassy material" when dry and a hydrogel when wetted with aqueous body fluids. 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.
  • 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). It is however within the scope of the invention for the body of the catheter to be of a different material which is coated with a polyurethane.
  • polyurethane e.g. Estane (Goodrich), Pellethane (Dow ) or Elastolan (BASF). It is however within the scope of the invention for the body of the catheter to be of a different material which is coated with a polyurethane.
  • the HPMA is bonded to the polyurethane surface of the body by means of residues of a di or higher functionality isocyanate compound.
  • This isocyanate compound may be aliphatic, aromatic or alicyclic.
  • suitable isocyanates are aliphatic diisocyanates having 2 to 10 carbon atoms, more preferably 5 to 7 carbon atoms.
  • a preferred aliphatic diisocyanate is hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • the preferred compound is pure HMDI.
  • HPMA coating may be applied to the polyurethane surface of the catheter body in a number of ways, examples of which are given below.
  • a solution of the isocyanate (eg. MDI) and KPMA 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 eg. 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 abovedescribed 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 (eg. 4-8 mins at 65-70oC; 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 soiuticn; so that isocyanate compound residues become bonded to the polyurethane, followed by dipping into a solution of the HPMA (the HPMA solution), preferably containing a catalyst for forming polyure thanes.
  • a solution of the isocyanate the isocyanate soiuticn; so that isocyanate compound residues become bonded to the polyurethane
  • HPMA the HPMA solution
  • 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 preferacly iess than 10 seconds.
  • the catheter is removed from the soiuticn and the solvent is allowed to evaporate in air prior to the catheter being dipped in the HPMA solution containing a polyurethane formation catalyst.
  • HPMA solution containing a polyurethane formation catalyst A suitable concentration range for the HPMA is
  • the preferred solvent is a mixture of DMF ( 50-75%) and THF
  • the polyurethane formation catalyst is preferably used in an amount of 1 part of catalyst per 500 -10000 parts of HPMA.
  • the catalyst may for example be stannous octoate. stannous chlorice. diethyl zinc. diphenyl zinc, and other common organometallic 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 minutes. 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.
  • Catheters in accordance with the invention may be kept within the body for 10-12 weeks without problem.
  • the HPMA coating may include an anti-microbial agent or a drug for delivery to the body of the patient, eg. copper or silver compounds, chlorhexidine or other antiseptic, or an antibiotic.

Abstract

The invention relates to a tubular device (other than a Foley balloon catheter for urine drainage purposes) for supplying fluid (gas or liquid) to, or removing fluid from, the body of a patient. According to the invention the tubular device comprises an elongate tubular body having one end for insertion in the body of a patient wherein at least over a portion of its length extending from the insertion end the exposed surface of the body is of a polyurethane and over said length the body is provided with a coating of poly(N-mono hydroxy)propyl methacrylamide) bonded to said polyurethane surface by residues of a di or higher functionality isocyanate compound.

Description

TUBULAR DEVICE WITH HYDROPHILIC SURFACE
The present invention relates to a tubular device (other than a Foley balloon catheter for urine drainage purposes; for supplying fluid (gas or liquid) to, or removing fluid from, the body of a patient.
Examples of tubular devices with which the present invention is concerned include catheters (eg. cardiovascular catheters and radiological catheters), and anaesthesia tubes (eg. endotrachial tubes). For convenience, all such devices are referred to herein as catheters.
To facilitate insertion and withdrawal of a catheter into the body, it is desirable that 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. In other words, the wetted surface should feel "slippery". Such a surface also minimises rubbing between the catheter and the body of the patient during residence of the catheter in the body and therefore minimises discomfort to the patient.
According to a first aspect of the present invention there is provided a catheter other than a Foley balloon catheter comprising an elongate tubular body having one end for insertion in the body of a patient wherein at least over a portion of its length extending from the insertion end the exposed surface of the body is of a polyurethane and over said length the body is provided with a coating of poly(N-(mono hydroxy)propyl methacrylamide ) bonded to said polyurethane surface by residues of a di or higher functionality isocyanate compound.
According to a second aspect of the present invention there is provided a method of producing a catheter as defined in the preceding paragraph comprising treating said exposed surface with a di or higher functionality isocyanate compound and with poly(X-(mono hydroxy)propyl methacrylamide) so that the latter is bonded to said surface by residues of the di or higher functionality isocyanate compound to form a coating on the surface.
Preferably the poly(N-(mono hydroxy)propyl methacrylamide) is poly(N-(2-hydroxy)propyl methacrylamide), although other isomers in which the hydroxy group is at a different position or. the prcpyl chain may be used. The invention will be specifically described with respect to poly(X-(2-hydroxy)propyl methacrylamide ) although the following description is applicable mutatis mutandis to the other isomers.
The poly(N-(2-hydroxy)propyl methacrylamide) (hereinafter referred to simply as HPMA) provides a coating which is a "glassy material" when dry and a hydrogel when wetted with aqueous body fluids. 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.
The HPMA provides several advantages. In particular, 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.
Preferably the HPMA has a molecular weight (Mn) of at least 20,000 daltons as measured by GPC using polystyrene standard calibration. The preferred Mn range is 50.000-150.000 daltons. Preferably, 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.
Preferably the body of the catheter is of polyurethane. e.g. Estane (Goodrich), Pellethane (Dow ) or Elastolan (BASF). It is however within the scope of the invention for the body of the catheter to be of a different material which is coated with a polyurethane.
The HPMA is bonded to the polyurethane surface of the body 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 2 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 HMDI.
The bonding of the HPMA coating to a polyurethane surface is illustrated somewhat schematically below.
Figure imgf000005_0001
Although the above illustration shows the isocyanate residue being bonded to a nitrogen atom of the HPMA, it is also possible it is bonded to a carbon atom.
The HPMA coating may be applied to the polyurethane surface of the catheter body in a number of ways, examples of which are given below.
In one method, a solution of the isocyanate ( eg. MDI) and KPMA is formulated in a suitable solvent. Typically the 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 eg. 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 abovedescribed 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 (eg. 4-8 mins at 65-70ºC; followed by drying (in a fan oven) for several hours at 50-70°C, (e.g. 3-8 hrs at 60°C).
In an alternative method of applying the HPMA coating, the length of the catheter is initially dipped into a solution of the isocyanate (the isocyanate soiuticn; so that isocyanate compound residues become bonded to the polyurethane, followed by dipping into a solution of the HPMA (the HPMA solution), preferably containing a catalyst for forming polyure thanes.
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 preferacly iess than 10 seconds.
After this dipping process, the catheter is removed from the soiuticn 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
(25-50%) 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 -10000 parts of HPMA. The catalyst may for example be stannous octoate. stannous chlorice. diethyl zinc. diphenyl zinc, and other common organometallic catalysts used in polyurethane formation reactions. This dipping process is preferably effected for less than 10 seconds.
Upon removal of the catheter from the HPMA solution, the catheter is dried preferably at a temperature of 65-70°C for 8-12 minutes. Finally the catheter is washed with water and dried in warm air.
As a result of the abovedescribed treatments, 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.
Catheters in accordance with the invention may be kept within the body for 10-12 weeks without problem.
If desired, the HPMA coating may include an anti-microbial agent or a drug for delivery to the body of the patient, eg. copper or silver compounds, chlorhexidine or other antiseptic, or an antibiotic.

Claims

Claims
1. Tubular device for supplying fluid to, or removing fluid from, the body of a patient comprising an elongate tubular body having one end for insertion in the body of a patient characterized in that at least over a portion of the length of the elongate tubular body extending from the insertion end the exposed surface of the body is of a polyurethane and over said length the body is provided with a coating of poly(N-(mono hydroxy) propyl methacrylamide) bonded to said polyurethane surface by residues of a di or higher functionality isocynate compound.
2. Tubular device according to claim 1, characterized in that the poly( N-( mono hydroxy)propyl methacrylamide) is poly(N-(2-hydroxy)propyl methacrylamide) or an other insomer in which the hydroxy group is at a different position on the propyl chain.
3. Method of producing a tubular device according to claim 1 or 2 characterized in treating said exposed surface with di or higher
funcitonality isocyanate compound and with poly(N-(mono hydroxy) propyl methacrylamide) so that the latter is bonded to said surface by residues of the di or higher functionality isocyanate compound to form a coating on the surface.
PCT/EP1992/000919 1991-04-25 1992-04-27 Tubular device with hydrophilic surface WO1992019290A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9109068.8 1991-04-25
GB919109068A GB9109068D0 (en) 1991-04-25 1991-04-25 Tubular device with hydrophilic surface

Publications (1)

Publication Number Publication Date
WO1992019290A1 true WO1992019290A1 (en) 1992-11-12

Family

ID=10694039

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/000919 WO1992019290A1 (en) 1991-04-25 1992-04-27 Tubular device with hydrophilic surface

Country Status (3)

Country Link
AU (1) AU1657492A (en)
GB (1) GB9109068D0 (en)
WO (1) WO1992019290A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869127A (en) * 1995-02-22 1999-02-09 Boston Scientific Corporation Method of providing a substrate with a bio-active/biocompatible coating
US6165156A (en) * 1996-04-02 2000-12-26 Avitar, Inc. Device and method for fastening a catheter
US6179817B1 (en) 1995-02-22 2001-01-30 Boston Scientific Corporation Hybrid coating for medical devices
US6197051B1 (en) 1997-06-18 2001-03-06 Boston Scientific Corporation Polycarbonate-polyurethane dispersions for thromobo-resistant coatings
US6723121B1 (en) 1997-06-18 2004-04-20 Scimed Life Systems, Inc. Polycarbonate-polyurethane dispersions for thrombo-resistant coatings
US7736362B2 (en) 2003-09-15 2010-06-15 Boston Scientific Scimed, Inc. Catheter balloons

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106004A1 (en) * 1981-05-18 1984-04-25 Astra Tech Aktiebolag Method of forming a hydrophilic coating on a substrate
EP0379156A2 (en) * 1989-01-17 1990-07-25 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Improved hydrophilic lubricious coatings
EP0166998B1 (en) * 1984-06-04 1991-05-08 TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION Medical instrument and method for making

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106004A1 (en) * 1981-05-18 1984-04-25 Astra Tech Aktiebolag Method of forming a hydrophilic coating on a substrate
EP0166998B1 (en) * 1984-06-04 1991-05-08 TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION Medical instrument and method for making
EP0379156A2 (en) * 1989-01-17 1990-07-25 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Improved hydrophilic lubricious coatings

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869127A (en) * 1995-02-22 1999-02-09 Boston Scientific Corporation Method of providing a substrate with a bio-active/biocompatible coating
US6099563A (en) * 1995-02-22 2000-08-08 Boston Scientific Corporation Substrates, particularly medical devices, provided with bio-active/biocompatible coatings
US6179817B1 (en) 1995-02-22 2001-01-30 Boston Scientific Corporation Hybrid coating for medical devices
US6165156A (en) * 1996-04-02 2000-12-26 Avitar, Inc. Device and method for fastening a catheter
US6197051B1 (en) 1997-06-18 2001-03-06 Boston Scientific Corporation Polycarbonate-polyurethane dispersions for thromobo-resistant coatings
US6723121B1 (en) 1997-06-18 2004-04-20 Scimed Life Systems, Inc. Polycarbonate-polyurethane dispersions for thrombo-resistant coatings
US7736362B2 (en) 2003-09-15 2010-06-15 Boston Scientific Scimed, Inc. Catheter balloons

Also Published As

Publication number Publication date
AU1657492A (en) 1992-12-21
GB9109068D0 (en) 1991-06-12

Similar Documents

Publication Publication Date Title
US5558900A (en) One-step thromboresistant, lubricious coating
EP0379156B1 (en) Improved hydrophilic lubricious coatings
EP0809541B1 (en) Process for producing commingled polyurethane-urea and poly(n-vinylpyrrolidone) polymer hydrogel coatings
US5849368A (en) Process for hydrophilicization of hydrophobic polymers
US6629961B1 (en) Medical device with hydrophilic coating
CA2211643C (en) Hydrogel coatings containing commingled structurally dissimilar polymer hydrogels
JP5054383B2 (en) Lubricating composition, method of preparation, and article coated thereby
US5302385A (en) Polyurethane-polyvinylpyrrolidone block copolymer and iodine carrier therefrom
JP2011514223A (en) Medical device with hydrophilic coating
JP3357065B2 (en) Hydrogel coating containing polyurethane-urea polymer hydrogel mixed with at least one other different polymer hydrogel
TW201002371A (en) Medical devices with hydrophilic coatings
WO1992019290A1 (en) Tubular device with hydrophilic surface
WO1992019289A1 (en) Treatment of polyurethane surfaces
JPH1024100A (en) Manufacture of medical article
WO1992019288A1 (en) Catheter having a coating on the exposed surface thereof
KR100458734B1 (en) Medical Device
CA2258077C (en) Hydrophilic interpenetrating polymer network coating for medical devices
JPH105325A (en) Medical utensils having easily slippable surface when wet and their production
JPH02220666A (en) Medical body insert jig having lubricating film and preparation thereof
MXPA98010584A (en) Med device

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA