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WO2000044812A2 - Polyoxyalcanes amino-fonctionnalises - Google Patents

Polyoxyalcanes amino-fonctionnalises Download PDF

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Publication number
WO2000044812A2
WO2000044812A2 PCT/EP2000/000544 EP0000544W WO0044812A2 WO 2000044812 A2 WO2000044812 A2 WO 2000044812A2 EP 0000544 W EP0000544 W EP 0000544W WO 0044812 A2 WO0044812 A2 WO 0044812A2
Authority
WO
WIPO (PCT)
Prior art keywords
amino
polyoxyalkanes
functionalized
branched
atoms
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2000/000544
Other languages
German (de)
English (en)
Other versions
WO2000044812A3 (fr
Inventor
Peter Ottersbach
Friedrich Sosna
Jan Feijen
Eva Katharina Klok-Lermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Creavis Gesellschaft fuer Technologie und Innovation mbH
Original Assignee
Creavis Gesellschaft fuer Technologie und Innovation mbH
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 Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical Creavis Gesellschaft fuer Technologie und Innovation mbH
Publication of WO2000044812A2 publication Critical patent/WO2000044812A2/fr
Publication of WO2000044812A3 publication Critical patent/WO2000044812A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

  • the invention relates to amino-functionalized polyoxyalkanes, a process for their preparation and their use.
  • Surfaces can also be modified by activating the surface by generating reactive groups.
  • ozonization of a polymer surface or its irradiation in the presence of oxygen to form oxidized reaction centers as z. B. in US 4311573, US 4589964 or EP 0378511, such a method.
  • Another method (described, for example, in EP 0574352) is based on plasma pretreatment of surfaces with the addition of oxygen to generate hydroperoxide groups, which in turn can function as reaction centers for downstream processes.
  • a plasma pretreatment process is described in US Pat. No. 4,731,156 that permits the immediate amino functionalization of surfaces.
  • spacer molecules such as, for example, decylamine hydrochloride (J Telden et al, J Biomater Be Polymer Edn, 4, 165-181, (1993)).
  • the spacer molecules ensure a greater separation of the functionality from the surface of the material to be modified
  • hydrophilic surfaces are often desired because they are physiologically harmless, are easy to clean or have bacteria-repellent properties.
  • amino groups have been retained as functional groups, since they not only have hydrophilic properties but also allow further reactions
  • An amino-functionalized coating of polymer substrates should have the following properties when using spacer molecules - hydrophilic chain segments
  • the object of the present invention was to provide a material for the amino functionalization of polymeric substrates which combines these properties
  • amino-functionalized polyoxyalkanes are outstandingly suitable for the production of coatings on polymeric substrates while maintaining an amino-functionalized substrate surface.
  • the present invention therefore relates to amino-functionalized polyoxyalkanes of the general formula
  • Amino-functionalized polyoxyalkanes according to the invention can be used for the surface treatment of polymeric substrates.
  • amino-functionalized polyoxyalkanes which have a simple structure are preferably used.
  • R branched or linear hydrocarbon chains with 1-30 C atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1-30 C atoms, or an aromatic hydrocarbon residue.
  • R monounsaturated hydrocarbon radical with 10 to 30 carbon atoms
  • the amino functionalized polyoxyalkanes can be covalently attached to a substrate, i. H.
  • the polyoxyalkanes according to the invention have an amino group, a polyoxyalkane backbone and other end groups, such as, for example, a long-chain ether or ester.
  • the pronounced bifunctionality of the polyoxyalkanes according to the invention makes it possible to use a polyoxyalkane derivative which has similar polarities at least at one chain end
  • the coating material is first applied to the substrate surface (physisorbed) and then immobilized using physical processes such as plasma activation.
  • good compatibility between the substrate surface and polyoxyalkane ensures a high number of pysisorbed molecules and thus a good coating layer in the immobilization step
  • the polyoxyalkanes according to the invention can also have hydrophilic and hydrophobic components at the same time.Therefore, uniform hydrophilizations of hydrophobic substrates can be made possible, which can otherwise only be achieved incompletely due to incompatibilities between coating material and substrate.
  • Polyoxyethylene stearyl ether amine is an example of such a compound since the stearyl radical a hydrophobic and the aminopolyoxyethylene chain has a hydrophilic character
  • polyoxyalkanes With the polyoxyalkanes according to the invention, surfaces of polymeric materials in particular can be gently aminofunctionalized, a change in the material properties of the surface by incorporating the amino groups into the material is prevented by the use of polyoxyalkanes as a spacer molecule Functionality is spatially separated from the surface via the spacer molecule
  • Another object of the present invention is a process for the preparation of amino-functionalized polyoxyalkanes of the general formula
  • a polyoxyethylene compound such as polyoxyethylene (20) stearyl ether (z. B. Brij®78 from DuPont) can be used.
  • the spacer molecule by known methods of organic chemistry, such as. B. the synthesis according to M. Mutter, Soluble Polymers in Organic Synthesis: I. Preparation of Polymer Reagents using Polyethylene Glycol with terminal Amino Groups as polymeric Component, Tetrahedron Lett. 31, 1978, 2839, amino functionalized.
  • An exemplary synthesis route is given in the examples.
  • a suitable solvent such as. B. chloroform
  • dissolved amino-functionalized polyoxyalkane can then be applied to a material surface or physisorbed.
  • the immobilization following the physisorption can be carried out by plasma treatment, microwave radiation, UV radiation, ⁇ -rays or corona treatment.
  • a plasma process is described as an example in the examples.
  • Another object of the present invention is the use of the amino-functionalized polyoxyalkanes for the surface coating of polymeric substrates, for the production of medical technology products or for the production of hygiene products or hygiene articles.
  • Medical technology products include catheters, blood bags, drainage, guide wires and surgical instruments, dialysis and oxygenator membranes, intraocular lenses and contact lenses.
  • Hygiene products include toothbrushes, toilet seats, combs and packaging materials.
  • the polyoxyalkanes according to the invention are particularly suitable for coating polymeric materials.
  • the mixtures to be coated do not have to consist entirely of a polymer; it is only important that the surface consists of a polymeric material which, for. B. undergoes grafting reactions with the polyoxyalkane under plasma conditions.
  • the polymeric substrates include homopolymers and copolymers, for example polyolefins, such as polyethylene (HDPE and LDPE), polypropylene, polyisobutylene, polybutadiene, polyisoprene, natural rubbers and polyethylene-co-propylene, and halogen-containing ones Polymers, such as polyvinyl chloride, polyvinylidene chloride, polychloroprene and polytetrafluoroethylene, polymers and copolymers of vinylaromatic monomers, such as polystyrene, polyvinyltoluene, polystyrene-co-vinyltoluene, polystyrene-co-acrylonitrile, polystyrene-co-butadiene-co-acrylonitrile, polycondensates, for example polyester, such as polyethylene terephthalate and polybutylene tere
  • amino-functionalized polyoxyalkanes according to the invention allow further functional groups to be applied to polymeric substrates.
  • carboxylate-containing substances such as polyacrylic acid as a spacer molecule
  • This can be done, for example, by reaction using N-hydroxysuccinimide ( NHS) and l-ethyl-3- (3-dimethylaminopropyl) carbodiimide (ECD)
  • carboxylic acid anhydrides such as maleic anhydride as carboxylic acid amide, so that a free carboxylic acid function results on the substrate surface
  • a polyethylene film is placed in a 1 w / v. -% solution of polyoxyethylene (20) - stearyl etheramine (product from Example 1) in chloroform. After 30 minutes, the film is removed and dried in vacuo at room temperature.
  • a polyethylene film is treated with a static argon plasma (48 watts) for 5 seconds, then rinsed with a 0.1 mM hydrochloric acid solution and distilled water. The film is then placed in a 1% by volume solution of polyoxyethylene (20) stearyl etheramine (from Example 1) in monomolar hydrochloric acid and ethanol in a weight ratio of 1: 1. After 30 minutes, the film is removed and dried in vacuo at room temperature.
  • the plasma treatment takes place in a tubular reactor (length 80 cm, inner diameter 6.5 cm).
  • the reactor is evacuated to a pressure of 10 mbar "5, then blanketed with argon. This procedure is repeated three times.
  • the reactor is evacuated again and an argon flow of 10 cm 3 min "1 is passed through the reactor. After 15 minutes the argon flow is stopped and the samples are treated with a static plasma (48 watt) for five seconds
  • An argon flow of 10 cm 3 min "1 is again passed through the reactor for a period of two minutes, after which the pressure is equalized with the surrounding air pressure with argon.
  • the samples are removed, turned over and the back of the samples is now treated like the front according to the procedure described.
  • the polyethylene films coated according to Example 4 are washed three times with 0.1 molar hydrochloric acid solution and three times with demineralized water, then dried in vacuo at room temperature.
  • polyacrylic acid M w 2000, Aldrich
  • NHS N-hydroxysuccinimide
  • PEO polyoxyethylene (20) stearyl etheramine
  • product from Example 1 50 mg of polyacrylic acid (M w 2000, Aldrich), 1.5 mg of N-hydroxysuccinimide (NHS) and 10.8 mg of polyoxyethylene (20) stearyl etheramine (product from Example 1) are dissolved in 2.5 ml of demineralized water.
  • 1 ml of a 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) stock solution with a concentration of 0.9 g / 1 is added every half hour.
  • the pH of the reaction solution is continuously checked and, if necessary, kept constant at 5.8-5.9 by adding 0.01 molar hydrochloric acid.
  • the pH of the reaction solution is adjusted to a value of 7.5 by adding 0.2 molar sodium hydroxide solution.
  • the reaction solution is dialyzed through a membrane (CE membrane, MWCO 6-8000, Spectra / Por®) against demineralized water. For complete cleaning, the solution is dialyzed once more at pH 11 and then freeze-dried.
  • a membrane CE membrane, MWCO 6-8000, Spectra / Por®
  • the pH of the reaction solution is adjusted to a value of 7.5 by adding 0.2 molar sodium hydroxide solution.
  • the reaction solution is dialyzed through a membrane (CE membrane, MWCO 6-8000, Spectra / Por®) against demineralized water. For complete cleaning, the solution is dialyzed once more at pH 11 and then freeze-dried.
  • a polyethylene film is treated in a static argon plasma (49 watts) for 3 seconds, then rinsed with a 0.1 mM hydrochloric acid solution.
  • the film is then placed in a 1% by weight solution of polyoxyethylene (20) stearyl ether polyacrylic acid (from Example 7) in monomolar hydrochloric acid and ethanol in a weight ratio of 1: 1. After 30 minutes, the film is removed and dried in vacuo at room temperature.
  • Plasma immobilization of a polyethylene film from Example 9 coated with polyoxyethylene (20) stearyl ether polyacrylic acid takes place in a tubular reactor (length 80 cm, inner diameter 6.5 cm). The reactor is evacuated to a pressure of 10 mbar '5, then blanketed with argon. This procedure is repeated three times. Then the polyethylene films coated with polyoxyethylene (20) stearyl ether polyacrylic acid are placed on a glass plate in the middle of the reactor. The reactor is evacuated again and an argon flow of 10 cm 3 min "1 is passed through the reactor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polyoxyalcanes amino-fonctionnalisés, de formule générale (I), dans laquelle n = 1-5; m = 5-100; a = 0,1; b = 0,1; R représente des chaînes hydrocarbonées linéaires ou ramifiées renfermant 1 à 30 atomes de C, des chaînes hydrocarbonées linéaires ou ramifiées, mono-oléfiniquement ou poly-oléfiniquement insaturées, renfermant 1 à 30 atomes de C, ou un résidu hydrocarboné aromatique; R' a la même signification ou une autre signification que R; X représente H, OH, NH2, F, Cl, Br, I, CN, NCO, SCN, CNO, NO2, NO, SH, CO2M, SO3M, SO4M, M étant H ou un métal alcalin; et X' a la même signification ou une autre signification que X, à condition que X ou X' soit NH2. L'invention concerne également un procédé permettant de produire lesdits polyoxyalcanes. Les polyoxyalcanes amino-fonctionnalisés de l'invention peuvent être utilisés pour revêtir la surface de substrats polymères.
PCT/EP2000/000544 1999-01-26 2000-01-25 Polyoxyalcanes amino-fonctionnalises Ceased WO2000044812A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19902942A DE19902942A1 (de) 1999-01-26 1999-01-26 Aminofunktionalisierte Polyoxyalkane
DE19902942.3 1999-01-26

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WO2000044812A2 true WO2000044812A2 (fr) 2000-08-03
WO2000044812A3 WO2000044812A3 (fr) 2000-11-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002080674A1 (fr) * 2001-04-06 2002-10-17 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de conservation antimicrobiens pour produits alimentaires

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0031210D0 (en) * 2000-12-21 2001-01-31 Victrex Mfg Ltd Bio-compatible polymeric materials
DE10110885A1 (de) * 2001-03-07 2002-09-12 Creavis Tech & Innovation Gmbh Mokrobizide Trennsysteme

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3608716A1 (de) * 1985-05-31 1986-12-04 Texaco Development Corp., White Plains, N.Y. Verfahren zur herstellung von polyoxyalkylen-polyaminen
JPH08143858A (ja) * 1994-11-25 1996-06-04 Toray Ind Inc 帯電防止剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002080674A1 (fr) * 2001-04-06 2002-10-17 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de conservation antimicrobiens pour produits alimentaires

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Publication number Publication date
WO2000044812A3 (fr) 2000-11-30
DE19902942A1 (de) 2000-07-27

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