WO2013030148A1 - Hydrophilic thermoplastic polyurethanes and use thereof in medical equipment - Google Patents

Hydrophilic thermoplastic polyurethanes and use thereof in medical equipment Download PDF

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Publication number
WO2013030148A1
WO2013030148A1 PCT/EP2012/066591 EP2012066591W WO2013030148A1 WO 2013030148 A1 WO2013030148 A1 WO 2013030148A1 EP 2012066591 W EP2012066591 W EP 2012066591W WO 2013030148 A1 WO2013030148 A1 WO 2013030148A1
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thermoplastic polyurethane
mol
isocyanate
characterized
glycol
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PCT/EP2012/066591
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German (de)
French (fr)
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Jürgen Köcher
Henricus Peerlings
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Bayer Intellectual Property Gmbh
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/283Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08Materials for coatings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3212Polyhydroxy compounds containing cycloaliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Abstract

The invention relates to a thermoplastic polyurethane that can be obtained by reacting at least the following components: a polyisocyanate having two isocyanate groups, a polycarbonate having two isocyanate-reactive groups, a chain extender having two isocyanate-reactive groups, and a polyoxyalkylene ether having an isocyanate-reactive group, wherein the ratio of the isocyanate groups of the polyisocyanate a) to the total of the isocyanate-reactive groups of the polycarbonate diol b), of the chain extender c), and of the polyoxyalkylene ether d) is in the range of 0.95 to 1.05:1. The invention further relates to a method for producing the thermoplastic polyurethane according to the invention and to a medical device that comprises a thermoplastic polyurethane according to the invention.

Description

Hydrophilic thermoplastic polyurethanes and their use for medical

The present invention relates to a thermoplastic polyurethane that is obtainable by reacting at least the following components: a polyisocyanate having two isocyanate groups, a polycarbonate having two isocyanate-reactive groups, a chain extenders with two isocyanate reactive groups, a polyoxyalkylene ether with an isocyanate-reactive Group. Further objects of the invention are a process for the preparation of the thermoplastic polyurethane according to the invention as well as a medical device that includes an inventive thermoplastic polyurethane. Medical devices such as catheters with hydrophilic surfaces offer many advantages. Thus, they are more easily wettable by water, which on the one hand reduces the friction when introduced into the body and on the other hand, increases the biocompatibility. Often hydrophilic surfaces are generated by coating with suitable polymers. However, the coatings company in an aqueous environment (tissue, blood, urine) may be very much water and swell while much stronger than the underlying substrate of the medical device. Due to the different swelling behavior may lead to a separation of the coating and substrate, which is associated with significant medical complications.

To avoid these complications, medical devices such as catheters may be prepared directly from an elastic, hydrophilic material. In this case, the risk of layer separation does not exist. As suitable materials for this purpose have been described (TPU) hydrophilic thermoplastic polyurethanes. These are usually composed of a long chain polyether, polyester or polycarbonate diol, a divalent short chain aliphatic alcohol and an aliphatic or aromatic diisocyanate. A hydrophilic finishing is effected by the use of a hydrophilic polyether. Example of these hydrophilic thermoplastic polyurethanes see CA 2017951 AI, CA 2017952 Al, US 4,789,720 and WO 8800214 Al in the patent applications WO 2007092303, US 2007/0078388 described. The presently disclosed polyurethanes include all polyether building blocks.

However, it has shown that the polyether-based polyurethanes have sufficiently high hydrauli- rophilie. Polyether based polyurethane ureas are known from the patent claims avoidance WO 2009 115 263 known. Although the compounds described herein are chemically stable, but this take relatively little water, based, for example, about 50% of water to the polymer weight. Further result from contact angle measurements of the compositions described herein, relatively high contact angle, so that, despite the use of a hydrophilic block, the surface of these materials is not sufficiently hydrophilic and thus poorly wettable.

More hydrophilic polyether-based TPU resins are known, for example from Lubrizol, Cleveland, OH, USA under the trade name "Tecophilic." Although many of these Materi- take alien large amounts of water, for example up to 1000% of its own weight, but lose these hydrogels because of the strong water absorption of stability, especially dimensional stability. this behavior is seen in part as unfavorably and limits the number of applications for these compounds.

It is an object of the present invention to provide a thermoplastic polyurethane for the manufacture of medical devices prepared which has a higher hydrophilicity than the known TPUs and it has good mechanical properties, in particular high elongation at break and tear strength.

This object is achieved by a polyurethane of the type mentioned, in which the ratio of the isocyanate groups of the polyisocyanate a) to the sum of isocyanate-reactive groups of the polycarbonate diol b), the chain extender c) and the polyoxyalkylene ether d) in the range 0, 95 to 1.05: 1.

In other words, the ratio of a is: (b + c + d) = 0.95 to 1.05: 1, wherein a, b, c and d for the respective starting materials a), b), c) and d) stand.

According to the invention it is provided that the polycarbonate has two isocyanate-reactive groups. This is advantageous because it is a linear polyurethane polymer is obtained which has thermoplastic properties of the present invention.

It can be used for the preparation of both aqueous dispersions, organic solutions as well as lk-Gießansätze well as other known to those skilled in formulations.

The individual components for the synthesis of the polyurethane of the invention will be explained in more detail below: a) polyisocyanate having two isocyanate groups

As polyisocyanates a) All known to those skilled aromatic, araliphatic, aliphatic and cycloaliphatic isocyanates having an average NCO functionality of 2 are used individually or in any mixtures with each other, it is irrelevant whether they have been prepared by phosgene or phosgene-free processes. These can also contain iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, Acylhamstoff- and / or carbodiimide structures. The polyisocyanates can be used individually or in any mixtures with one another.

Isocyanates from the series of aliphatic or cycloaliphatic representatives preferably set once, which comprise a carbon backbone (without the NCO groups) of from 3 to 30, preferably 4 to 20 carbon atoms.

Particularly preferred compounds of component (a) in accordance with the above-mentioned type having aliphatically and / or cycloaliphatically bound isocyanate groups such as bis (isocyanatoalkyl) ether, bis (isocyanatoalkyl) benzenes, -toluenes and -xylenes, propane diisocyanates, butane, pentane diisocyanates, hexane diisocyanates (such as hexamethylene diisocyanate, HDI), Heptandiisocyanate, Octandiisocyanate, Nonandiisocyanate (for example, trimethyl-HDI (TMDI) generally as a mixture of 2,4,4- and 2,2,4-isomers), Dekandiisocyanate, Dekantriisocyanate, unde - kandiisocyanate, Undekantriisocyanate, dodecane diisocyanates, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane (HfrXDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis- (4-isocyanatocyclohexyl) methane (H 12 MDI) or bis (isocyanatomethyl) norbornane (NBDI).

Very particularly preferred compounds of component (a) include hexamethylene diisocyanate (HDI), trimethyl-HDI (TMDI), 2-methylpentane-l, 5-diisocyanate (MPDI), isophorone diisocyanate (IPDI), 1,3- and l, 4-bis (isocyanatomethyl) cyclohexane (H east XDI), bis (isocyanatomethyl) norbornane (NBDI), 3 (4) -isocyanatomethyl-l-methyl-cyclohexyl isocyanate (IMCI) and / or 4,4'-bis- (isocyanatocyclohexyl) methane (H 12 MDI) or mixtures of these isocyanates. b) polycarbonate having two isocyanate-reactive groups

The polyurethaneurea according to the invention comprises units which originate from at least one polycarbonate, the hydroxyl group bears (polycarbonate). In principle, suitable for the introduction of units based on the hydroxyl group-containing polycarbonate are polycarbonate polyols, ie, polyhydroxy compounds having an average hydro xylfunktionalität of 1.7 to 2.3, preferably from 1.8 to 2.2, particularly preferably from 1.9 to 2.1, most preferably about 2.0. The polycarbonate is therefore preferably substantially linear. Suitable hydroxyl-containing polycarbonates are polycarbonates of a molecular weight (on the OH number of specific molecular weight; DIN 53240) of preferably 400 to 6000 g / mol, more preferably 500 to 5000 g / mol, in particular from 600 to 3000 g / mol in question are obtained for example by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene with polyols, preferably diols. As such diols for example ethylene glycol, 1, 2- and 1, 3-propanediol, 1, 3- and 1, 4-butanediol, 1, 6-hexanediol, 1, 8- octanediol, neopentyl glycol, 1, 4-bis-hydroxymethyl cyclohexane, 2 methyl-l, 3-propanediol, 2,2,4-trimethylpentane-l, 3-diol, di-, tri- or tetraethylene glycol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A and also lactone-modified diols in question.

The diol component preferably contains 40 to 100 wt .-% of hexanediol, preferably 1, 6-hexanediol and / or hexanediol derivatives, preferably those which in addition to terminal OH groups of ether or ester groups, for example, products obtained by reacting 1 mol of hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone or by etherifying hexanediol with itself to give di- or tri-hexylene glycol were obtained. Polyether-polycarbonate diols can be used. The hydroxyl polycarbonates should be substantially linear. Such polyvinyl lycarbonate are preferred on the basis of hexanediol 1, 6, and modifying action, co-diols such. As butanediol-1, 4, or also from ε-caprolactone. Further preferred polycarbonate diols are those based on mixtures of hexanediol-1, 6 and butane-1; 4. c) chain extender having two isocyanate reactive groups

The polyurethaneurea according to the invention has units which originate from at least one diamine or an amino alcohol or a diol. To produce the thermoplastic polyurethanes of the invention known as chain extenders (c) are used. Such chain extenders are diamines as well as hydrazides, such as hydrazine, 1, 2-ethylenediamine, 1, 2- and 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, iso- phorondiamin, mixture of isomers of 2,2 , 4- and 2,4,4-trimethylhexamethylenediamine, 2-methyl pentamethylene diamine, diethylene triamine, 1, 3- and 1, 4-xylylenediamine, α, α, α ', α'-tetramethyl-1, 3- and -1, 4 -xylylenediamine and 4,4-diaminodicyclohexylmethane, dimethylethylenediamine, hydrazine, adipic acid dihydrazide, 1, 4-bis (aminomethyl) cyclohexane, 4,4'-diamino-3,3 '- dimethyldicyclohexylmethane and other (Ci-C i) -di - and Tetraalkyldicyclohexylmethane such as 4,4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldicyclohexylmethan.

As diamines or amino alcohols in general are also low molecular weight diamines or aminoalcohols which contain active hydrogen with respect to NCO groups of different reactivity include, such as compounds which, besides a primary amino group and secondary amino groups or, besides an amino (primary or secondary), also OH comprise groups. Examples include primary and secondary amines such as 3-amino-l -Methylaminopropan, 3-amino-1 -Ethylaminopropan, 3-amino-l-cyclohexylaminopropane, 3-amino-l-methylamino, further amino alcohols such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine and particularly preferably diethanolamine.

Furthermore, can be used diols as chain extenders c). The molecular weight is preferably 62 to 500 g / mol, particularly preferably 62 to 400 g / mol, in particular 62 to 200 g / mol.

Suitable polyols may contain aliphatic, alicyclic or aromatic groups. Mentioned here are, for example, the low molecular weight polyols having up to about 20 carbon atoms per molecule such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1, 4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1, 4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) , Ester diols such as a- hydroxybutyl-s-hydroxy-caproic acid ester, ro-hydroxyhexyl-y-hydroxybutyric acid ester, adipic re- (.beta.-hydroxyethyl) ester or terephthalic acid bis (.beta.-hydroxyethyl) ester may be used. d) polyoxyalkylene ether with an isocyanate-reactive group

The polyurethaneurea according to the invention comprises units which go back to a copolymer of polyethylene oxide and polypropylene oxide. These copolymer units are present in the polyurethane urea as end groups.

Nonionically hydrophilicizing compounds (d) are for example monohydric, the statistical co-tel 5 to 70, preferably 7 to 55 ethylene oxide units per molecule Polyalkylenoxidpo- lyetheralkohole, as are obtainable by alkoxylation of suitable starter molecules in known manner (for example, in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Volume 19, Verlag Chemie, Weinheim p 31-38).

Suitable starter molecules are, for example, saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octa- nole and nonanols, n-decanol, n-dodecanol, n-tetradecanol , n-hexadecanol, n-octadecanol, lohexanol Cyc-, the isomeric methylcyclohexanols or hydroxymethylcyclohexane hydroxymethyloxetane, 3-ethyl-3- or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1- dimethylallyl alcohol or oleyl alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisyl alcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, Dibutyla- min, bis (2-ethylhexyl) -amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine, and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or IH-pyrazole. Preferred starter molecules are saturated monoalcohols. Diethylenglykolmo- is particularly preferred nobutylether used as a starter molecule. The alkylene oxides of ethylene oxide and propylene oxide may be used in any order or else in a mixture for the alkoxylation reaction.

The polyalkylene oxide is mixed polyalkylene oxide polyethers of ethylene oxide and propylene oxide, the alkylene oxide units preferably consist of at least 30 mole%>, more preferably at least 40 mol% of ethylene oxide units. Preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers at least 40 mol% of ethylene and up to 60 mol% of propylene oxide units.

The average molecular weight of the polyoxyalkylene ether is preferably 500 g / mol to 5000 g / mol, particularly preferably from 1000 g / mol to 4000 g / mol, in particular 1000 to 3000 g / mol.

In addition to the above-mentioned substances according to the invention can also be provided that tri- to a lesser extent or higher-functional raw materials a)) and / or c) are used b. The amounts used are, however, be set so that thermoplastic processing of the material is still possible.

For the stoichiometry of the reactions:

The ratio of the equivalents of isocyanate groups used and the sum of Equiva- lente all isocyanate-reactive groups used (NEH, OH) should lie between 0.95 and 1.05. it deviates from these conditions, you get products, as evidenced in the examples section with reference to comparative examples, can no longer be processed by a thermoplastic.

The ratios of isocyanate-reactive components are shown to each other as follows:

From 0.01 to 0.05 mol polyoxyalkylene d) per mol of polycarbonate diol a), preferably 0.03 to 0.4 mol polyoxyalkylene d) per mol of polycarbonate diol a), very particularly preferably 0.05 to 0.25 mol polyoxyalkylene d) per mol polycarbonate diol a),

0.2 to 4.0 mol of chain extenders c) per mol of polycarbonate diol b), preferably 0.5 to 3.0 mol of chain extenders c) per mol of polycarbonate diol b), very particularly preferably 0.8 to 2.5 mol of chain extenders c ) per mol of polycarbonate diol b). The structure of the thermoplastic polyurethane elastomers can be done in several ways. So diol-extended materials, for example, according to the so-called "one-shot" method are made. In this process, all components are mixed in the melt and reacted with each other. Another known method is the two-stage "prepolymer" process, in which from the macrodiol, the monofunctional polyether alcohol and the isocyanate component is a pre-adduct which is reacted in a second step with the chain extender to give the polyurethane is formed.

The reaction of aliphatic amines runs even at room temperature so quickly that a homogeneous reaction is carried out in the melt is no longer possible because of the immediate precipitation of urea. Such polyurethaneureas are preferably produced in organic solution, as described in DE 31 34 112 Al, the disclosure of which is hereby incorporated into the present application. The polycarbonate diol b) and the polyoxyalkylene d) are first reacted with the isocyanate component a) to form a prepolymer, which is then dissolved in an organic solvent such as toluene and alcohol. The structure of the polymer is then accomplished by reaction with the dissolved in an organic solvent such as an alcohol chain extender c). This procedure is particularly suitable for diamines selected from chain extenders c). The polyurethane can then by removal of the solvent, for example be obtained by drying and then further processed for example by extrusion or injection molding. However, the preparation of the polymers according to the invention is not limited to the aforementioned methods. Thus, the polymers can also continuously for a belt process, as described in GB 1,057,018 and an extrusion process, such as for example in DE 19 64 834 Al discloses, are prepared. In the case of the preparation of polyurethane ureas itself provides the method described in DE 24 23 764 AI to particularly. In addition, the erfindungsgemä- SEN polyurethanes can be prepared as a dispersion, in particular via the per se known acetone process.

To accelerate the reaction rate of the reactant mixture may be added advantageously, one or more catalysts. This is especially true for the use of DIO len as chain c). Suitable catalysts are those of the prior art ten well-known and conventional tertiary amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, Ν, Ν'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, Diazabicyc- lo [2,2 2] octane and the like, and in particular, organic metal compounds such as titanic acid esters, bismuth, iron compounds or tin compounds such as tin dioctoate, dilaurate or the dialkyltin salts of aliphatic carboxylic acids such as dibutyltin diacetate or dibutyltin dilaurate or the like. Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron, tin, zirconium and bismuth compounds. The total amount of catalysts in the inventive TPU is usually preferably 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total amount of TPU. In the case of the use of diamines as chain extenders c) can be dispensed with the use of a catalyst.

The polyurethanes and polyurethane-ureas of the invention can - preferably 0.1 - be used in waxes, antioxidants, separating agents and / or UV absorbers with - 3 wt% (based on the total amount of all components). Is a subsequent use of the inventive polymers provided in the medical field should, if at all, only minimum necessary amounts of such additives are used, so that the cell compatibility is not affected.

Antioxidants can all this known products as such. are as described in EP-A describes 12343, are used. Antioxidants based on sterically hindered phenols, such are preferred. B. 2,6-di-t-butyl-4-methyphenol and derivatives (commercial products of Irganox series, BASF).

In preparing the novel thermoplastic polyurethanes usual antistatic agents, flame retardants, fillers and dye coating can be added in principle. In the case of a medical application of the polymer, however, should avoid the use of these additives.

In order to improve the processability of the polyurethane of the invention in an extruder, the invention can polyurethane one or more release agents can be added. Especially preferred for this purpose the use of Licowachs E Clariant is.

Examples

The invention will be further illustrated by the following examples.

methods:

Tear strength: The tear strength was determined according to EN ISO 527-3 with a test piece type 5 with a thickness of 2 mm at a tensile speed of 200 mm / min.

Solution viscosity (LV):

To measure the solution viscosity 99.7 g of N-methyl-2-pyrrolidone with 0.1% dibutylamine and 0.4 g of the particular TPU granules were weighed. The samples thus prepared were stirred on egg nem magnetic stirrer. TPU samples were dissolved at room temperature and allowed to stand overnight. The samples and a blank value (pure solvent) were recorded on a Schott viscosity measuring station Fa at 25 ° C. Measured. . The viscosity measuring station from the company Schott consisting of: viscosity measuring station AVS 400, measuring stand ASV / S, glass thermostat, Ubbelohde viscometer type 50110. The relative solution viscosity is calculated by dividing by the time (solvent) from the time (solution).

MVR value:

The MVR value of the granules was measured according to ISO 1133 with 10 kg weight. NCO content:

The determination of the NCO content of the resins described in the examples and comparative examples by titration in accordance with DIN EN ISO 11,909th

Average particle size:

The mean particle sizes of the polyurethane dispersions are using a Laserdiffratometers "High Performance Particle Sizer HPPS", type HPP performed 5002 from Malvern Instruments GmbH, Herrenberg, Germany. For measurement, the sample was highly diluted in the form of an aqueous dispersion initially. For this purpose, about 1 μΐ aqueous crude dispersion in 1 ml of water and fed to the thus-diluted dispersion of the solids content measurement.:

The determination of the solids contents were according to DIN-EN ISO 3251. It was added 1 g of polyurethane dispersion at 115 ° C to constant weight (15-20 min) using an infrared dryer. Production of press plates:

For the manufacture of press plates from the inventive polymer a dispersion of the polymer was first dried and then granulated. This granulate was then transferred to a heatable hydraulic press "Polystat 200 T" from the company Servitec machines Service GmbH, Wustermark, DE, at 230 ° C and pressed to 200 bar have been wherein the granules depressurized melted for 5 minutes at 230 ° C and then for 5 min. It was then cooled while maintaining the pressure to below 100 ° C.

Contact Angle Measurement

On the surface of the dried polymer dispersions or on the surfaces of the respective press plates measuring static water contact angles were carried out. Initially was removed any existing static charge of the sample surface by means of an antistatic drier. Then, the company Data Physics were set up with the computer-controlled spraying 10 drops of Millipore water to the surfaces by means of a video contact angle instrument OCA20 and the static wetting angle measured.

List of substances used:

Desmophen C2200: polycarbonate polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)

Polyether PW 56: polyethylene glycol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)

Polyether LB 25: (monofunctional polyether based on ethylene oxide propylene oxide number average molecular weight 2,250 g / mol, OH number 25 mg KOH / g (Bayer MaterialScience AG, Leverkusen, DE)

definitions:

As a measure the ratio of the isocyanate groups of the polyisocyanate a) to the sum of isocyanate-reactive groups of the polycarbonate diol b), the chain extender is present c) and the polyoxyalkylene ether d) is considered, in other words, the ratio of a: (b + c + d)

Examples 1-4: products with diols as chain

Example 1 (inventive)

488.5 g of polycarbonate diol C Desmophen 2200, 75.0 g of the polyether LB 25, 49.3 g cyclohexanone ndimethanol were prepared at 130 ° C and 139.0 g of isophorone diisocyanate were added. The reaction onsgemisch was heated to 150 ° C and stirred at this temperature. After 10 min, the maximum viscosity was reached and the mixture is poured into a preheated to 80 ° C aluminum shell. The product was then stored for 2 hours at 90 ° C. The material was then granulated.

This ratio is 1.04. Example 2 (Comparative)

In comparison to inventive Example 1, this product contains as an end group of the polymer chain, the short-chain butyl glycol in place of the long-chain polyether LB 25 The resulting during installation short-chain monoether block results in an overall less hydrophilic polymer in comparison to Example 1. 977 g of the polycarbonate diol Desmophen C 2200 7.9 g of butyl glycol, 98.6 g of cyclohexanedimethanol were charged at 130 ° C and 278.0 g of isophorone diisocyanate were added. The reaction mixture was heated to 150 ° C and stirred at this temperature. After 20 min, the maximum viscosity was reached and the mixture is poured into a preheated to 80 ° C aluminum shell. The product was then stored for 2 hours at 90 ° C. The material was then granulated.

This ratio is 1.04. EXAMPLE 3 (COMPARISON)

Compared to the inventive Example 1, this product contains as end the hydrophobic 1 - octanol. A portion of the polycarbonate diol Desmophen C 2200 has been replaced by the hydrophilic polyether PW 56th By this partial replacement of Desmophen C 2200 by the polyether PW 56, the hydrophilicity of the polymer obtained is increased as a whole, wherein the hydrophilicity only a total does not increase, however, in the terminal. So this experiment shows the influence of the hydrophilic nature of the end group in comparison example 1.

841.2 g of the polycarbonate diol Desmophen C 2200, 136 g of the polyether diol PW 56, 8.6 g of 1-octanol, 98.6 g of cyclohexanedimethanol were charged at 130 ° C and 278.0 g of isophorone diisocyanate were added. The reaction mixture was heated to 150 ° C and stirred at this temperature. After 35 min, the maximum viscosity was reached and the mixture is poured into a preheated to 80 ° C aluminum shell. The product was then stored for 2 hours at 90 ° C. The material was then granulated. This ratio is 1.01.

In the following Table 1 the compositions of Examples 1 -3 and the ratios are the resulting again summarized:

Figure imgf000014_0001

Table 1: Summary of the stoichiometry of the experimental examples 1 -3

Example 4: Physical characterization

Of the granules of Examples 1 -3 press plates were manufactured made according to the method described above and tested for its physical and mechanical properties. The following Table 2 summarizes the test results together:

Figure imgf000014_0002

Table 2: Physical properties of the thermoplastic polyurethanes of Examples 1-3 As Table 2 shows the physical properties of the inventive product with the properties of the two comparative products are equal. However, the inventive product of Example 1 shows a relatively low water contact angle is thus substantially better wasserbe- wettable than the comparative products. The interpretation of the results also shows that a longer polyether must be installed in the molecule as an end. Butyl glycol can be regarded as short-chain Polyetherbaustein. Here, the water contact angle is significantly higher.

In Example 3, a hydrophobic end group in the polyurethane was used with 1-octanol. The hy- rophilie was adjusted by replacing a part of the Desmophens C 2200 through the hydrophilic polyether-ol PW 56th Due to the diol structure of this hydrophilic product is incorporated into the polymer chain, while material of the invention contains the hydrophilic polyether as an end group. The comparison of the water contact angle clearly shows that the incorporation of the hydrophilic group as in Example 3 has in the polymer chain no positive effect on the water contact angle. Example 1 clearly shows that only the inventive material with a hydrophilic polyether is easily wettable as an end group because of the low water contact angle.

EXAMPLES 5-8: Products with diamines as chain extenders Example 5 (inventive)

488.5 g Desmophen C 2200, 75.0 g LB 25 and 139.5 g of isophorone diisocyanate (IPDI) were reacted at 110 ° C until a constant NCO content of 4.2%. It was cooled and diluted with 875.0 g of toluene and 500 g of isopropanol. At room temperature, a solution of 58.1 g iso phorondiamin was added to 263.0 g of 1 -Methoxypropanol-2. After When the molecular weight that could be recognized by the end of the viscosity build of the batch was stirred for a further 20 hours to block the remaining free isocyanate groups with iso-propanol. 2399.1 g of a 32.2% was obtained solution of polyurethaneurea in toluene / iso-propanol / 1-methoxy-2 having a viscosity of 48200 mPas at 23 ° C. 2000 g of the resulting solution were poured into aluminum trays and dried, then granulating the obtained polyurethane.

This ratio is 1.04. Example 6 (Comparative)

In comparison to inventive Example 5, this product contains as an end group of the polymer chain, the short-chain butyl glycol in place of the long-chain polyether LB 25 The resulting during installation short-chain monoether block results in an overall less hydrophilic polymer in comparison to Example 5. Fig.

488.5 g Desmophen C 2200, 4 g of butyl glycol and 139.0 g of isophorone diisocyanate (IPDI) were reacted at 110 ° C until a constant NCO content of 4.7%. It was cooled and diluted with 875.0 g of toluene and 500 g of isopropanol. At room temperature, a solution of 58.1 g of isophoronediamine in 263.0 g of 1-2 -Methoxypropanol added. After the end of the Molge- wichtes and achieving the desired viscosity range, stirring was continued for 20 hours to block the remaining free isocyanate groups with isopropanol. 2327.6 g of a 30.1% was obtained solution of polyurethaneurea in toluene / iso-propanol / l-methoxypropan-2 having a viscosity of 16800 mPas at 23 ° C. 2000 g of the resulting solution were poured into aluminum trays and dried, then granulating the obtained polyurethane.

This ratio is 1.01.

Example 7 (COMPARISON)

Compared to the inventive Example 5, this product contains as end the hydrophobic 1 - octanol. A portion of the polycarbonate diol Desmophen C 2200 has been replaced by the hydrophilic polyether PW 56th By this partial replacement of Desmophen C 2200 by the polyether PW 56, the hydrophilicity of the polymer obtained is increased as a whole, wherein the hydrophilicity only a total does not increase, however, in the terminal. So this experiment shows the influence of the hydrophilic nature of the end group as compared with Example 5. 420.6 g Desmophen C 2200, 68.0 g of polyether PW 56, 4.3 g of 1-octanol and 139.0 g of isophorone diisocyanate (IPDI) were at 110 ° C until a constant NCO content of 4.8% converted. It was cooled and diluted with 875.0 g of toluene and 500 g of isopropanol. At room temperature, a solution of 58.1 g of isophoronediamine in 263.0 g of 1-2 -Methoxypropanol added. After the end of the molecular weight and achieve the desired viscosity range, stirring was WEI tere 20 hours to block the remaining free isocyanate groups with isopropanol. 2328.0 g of a 30.0% was obtained solution of polyurethaneurea in toluene / iso-propanol / 1-methoxy-2 having a viscosity of 680 mPas at 23 ° C. 2000 g of the resulting solution were poured into aluminum trays and dried, then granulating the obtained polyurethane.

The key figure beträgtl, 04th In the following Table 3, the compositions of Examples 5-7 as well as the ratios resulting are again summarized:

Figure imgf000017_0001

Table 3: Summary of the stoichiometry of the experimental examples 5-7

Example 8: Physical characterization of the granules of Examples 5-7 press plates were prepared according to the method described above and tested for its physical and mechanical properties. The following Table 4 summarizes the test results together:

Figure imgf000017_0002

Table 4: Physical properties of the thermoplastic polyurethanes of Examples 5-7

As Table 4 shows the mechanical properties of the inventive product with the properties of the two comparative products are equal. However, the inventive product of Example 5 shows a relatively low water contact angle and thus is much better wettable by water than the comparative products. The analysis of the results also shows that is advantageous to incorporate as an end a long polyether group into the molecule. Thus causes to be regarded as more short-chain Polyetherbaustein butylglycol that a polyurethane with significantly higher water contact angle is obtained.

In Example 7, a hydrophobic end group has been incorporated into the polyurethane with 1-octanol. The necessary hydrophilicity was adjusted by replacing a part of the Desmophens C 2200 by the hydrophilic polyether PW 56th Because of its diol structure, this compound is incorporated into the polymer chain, whereas material of the invention has hydrophilic polyether as an end group. The comparison of the water contact angle clearly shows that the incorporation of hydrophilic groups as in Example 7 has in the polymer chain no positive effect on the water contact angle. Example 5, however, shows that the inventive material has a low water contact angle with a hydrophilic polyether as a terminal group and is well wettable.

Example 9 (inventive)

488.5 g Desmophen C 2200, 75.0 g LB 25 and 139.5 g of isophorone diisocyanate (IPDI) were reacted at 110 ° C until a constant NCO content of 4.3%. It was cooled and diluted with 875.0 g of toluene and 500 g of isopropanol. At room temperature, a solution of 58.1 g iso phorondiamin was added to 263.0 g of 1 -Methoxypropanol-2. After the end of the molecular weight and achieve the desired viscosity range, stirring was continued for 5 hours to block the remaining isocyanate content with isopropanol. 2399.1 g of a 32.3% by weight was obtained polyvinyl lyurethanharnstofflösung in toluene / iso-propanol / 1 -Methoxypropanol-2 having a viscosity of 20400 mPas at 23 ° C. 2000 g of the resulting solution were poured into aluminum trays and dried, then granulating the obtained polyurethane.

This ratio is 1.04.

Example 10: Physical characterization of the inventive material of Example 9 and comparison with two commercial thermoplastic polyurethanes

Of the polyurethane of Examples 9, the melt viscosity (MVR) and the relative solution viscosity of the granules and of the strand resulting from the study of the melt viscosity was determined. Additionally, press plates were prepared as described initially at 230 ° C to perform tensile tests herewith. As a comparison, the same tests with the commercial products Desmopan 6580 A and Impranil ELH Bayer MaterialScience AG have been carried out. Table 5 below summarizes the results:

Product Example Desmopan 6580 Impranil ELH 9 A

LösungsvisGranulat 1.271 1.622 1.259 viscosity by

LösungsvisMVR strand 1,244 1,429 1,259 viscosity by

LösungsvisPressplatte 1.224 1.339 1.233 viscosity by

230 ° C

MVR 5 min; 10 kilograms, 7.79 19.6

(Ml / 10 min) 190 ° C

MVR 5 min; 10 kilograms, 23

(Ml / 10 min) 200 ° C

MVR 5 min; 10 kilograms, 10

(Ml / 10 min) 220 ° C

Elongation at break (%) pressing plate 414 596 351 230 ° C

Tenacity press plate 20.4 14.7 30.5

(MPa)

230 ° C

Voltage 100% press plate 2.94 3.7 8.4

(MPa) 230 ° C

Voltage 300% press plate 11.9 6.4 26.5

(MPa)

230 ° C

Contact angle <10 75 72

table 5

The investigation results show that the inventive material can be processed thermoplastically and found that the properties fall within the range of commercially available thermoplastic polyurethanes. Example 11 (comparison)

277.2 g Desmophen C 2200, 33.1 g of polyether LB 25 and 6.7 g of neopentyl glycol were introduced at 65 ° C and homogenized for 5 min with stirring. Was added to this mixture at 65 ° C within 1 minute first with 71.3 g of 4,4'-bis phorondiisocyanat (isocyanatocyclohexyl) methane (H 12 MDI) and then 11.9 g of iso. The mixture was heated at 1 10 ° C. the theoretical NCO value was after 3 hours 40 minutes is reached. The finished prepolymer was dissolved at 50 ° C in 711 g of acetone and then added at 40 ° C a solution of 4.8 g of ethylenediamine in 16 g of water within 10 min. The Nachrühr- time was 15 minutes. Subsequently pergiert within 15 min by addition of 590 g of water dis-. It was followed by removal of the solvent by vacuum distillation. To give a storage-stable polyurethane dispersion with a solids content of 39.1% and an average partial size of from 143 nm obtained. 220 g of the dispersion obtained were poured into aluminum trays and dried, then granulating the obtained polyurethane.

This ratio is 1.12. Example 12: Physical characterization of the material according to Example 11

For the polyurethane of Example 11, the melt viscosity (MVR) and the relative solution viscosity of the granules and of the strand resulting from the study of the melt viscosity was determined.

Solution viscosity solution viscosity Example MVR Rel. Rel.

(Pellets) (MVR strand)

(190 ° C)

Figure imgf000021_0001

table 6

The value of the solution viscosity determined is that due to the high ratio that resulted from a significant isocyanate excess, unwanted three-dimensional crosslinking had occurred. The solution viscosity of the MVR-Stange had reduced significantly. As a result, loading it indicated that the material of Comparative Example 11, was processed worse thermoplastic.

Experiment 13 (Comparison)

494.8 g of the polycarbonate diol Desmophen C 2200, 75.0 g of the polyether LB 25, 49.3 g cyclohexanone ndimethanol were prepared at 130 ° C and 117.0 g of isophorone diisocyanate were added. The reaction was heated onsgemisch immediately to 150 ° C by the exotherm, the reaction temperature rose to 175 ° C. The mixture was stirred 1 h at this temperature and the mixture poured onto a pre-heated to 80 ° C aluminum shell. The product was then stored for 2 hours at 90 ° C. Pieces of the poured polyurethane were ground in a mill. Due to the chosen Isocyanatunterschusses based on the hydroxyl groups of the material was so soft that it could not be milled. The product began to melt in the mill so that no granulation came about through the slightly elevated temperatures.

This ratio is 0.86.

Claims

claims
1. A thermoplastic polyurethane obtainable by reacting at least the following components: a) a polyisocyanate having two isocyanate groups, b) a polycarbonate having two isocyanate-reactive groups, c) chain extenders having two isocyanate-reactive groups, d) a polyoxyalkylene ether with an isocyanate-reactive group, characterized in that the ratio of isocyanate groups of the polyisocyanate a) to the sum of isocyanate-reactive groups of the polycarbonate diol b), the chain extender c) and the polyoxyalkylene ether d) in the range from 0.95 to 1 , 05: 1.
2. A thermoplastic polyurethane according to claim 1, characterized in that the polyisocyanate a) one or more compounds selected from the group hexamethyl endiisocyanat, trimethylhexamethylene diisocyanate, 2-methylpentane-l, 5-diisocyanate, phorondiisocyanat iso-, 1,3- and / or l, 4-bis (isocyanatomethyl) cyclohexane, bis (isocyanatomethyl) norbornane, 3 (4) -methyl-cyclohexyl isocyanate -Isocyanatomethyl- 1, 4,4'-bis methane (isocyanatocyclohexyl) or derivatives thereof having a uretdione, isocyanurate, is urethane, iminooxadiazinedione and / or Oxadiazmtrionstruktur with two NCO groups.
3. A thermoplastic polyurethane according to any one of claims 1 or 2, characterized in that the polycarbonate b) by reaction of at least one carbonic acid derivative in particular selected from the group consisting of diphenyl carbonate, dimethyl carbonate, phosgene and a diol selected in particular from the group of ethylene glycol, 1,2-propanediol , 1,3-propanediol, 1,3- butanediol, 1, 4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1, 4-bis-hydroxymethyl cyclohexane, 2-methyl-l, 3- propanediol, 2 , 2,4-trimethyl-l, 3-diol, diethylene glycol, triethylene glycol, tetra ethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, Polybutylengly- glycols, bisphenol A, tetrabromobisphenol A is available.
4. A thermoplastic polyurethane according to any one of claims 1 to 3, characterized in that the polycarbonate b) has a number average molecular weight of 400 to 6000 g / mol, preferably from 500 to 5000 g / mol and particularly preferably from 600 to 3000 g / mol ,
5. The thermoplastic polyurethane according to any one of claims 1 to 4, characterized in that the isocyanate-reactive groups of the polycarbonate b) and / or the chain extender c) and / or the polyoxyalkylene ether d) amino and / or hydroxy groups.
6. A thermoplastic polyurethane according to any one of claims 1 to 5, characterized in that the chain extender c) one or more compounds selected from the group of hydrazine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomer mixtures of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methyl pentamethylene diamine, diethylenetriamine, 1,3- and 1, 4-xylylene, a, a, a ', a '-tetramethyl-l, 3- and -1,4-xylylene diamine and 4,4'-diaminodicyclohexylmethane, dimethylethylenediamine, adipic acid dihydrazide, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diamino-3,3' -dimethyldicyclohexylmethan ,, N- aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine, ethanolamine Dietha-, Ethyenglykol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1, 4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, hydroquinone nondihydroxyethylether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) is.
7. The thermoplastic polyurethane according to any one of claims 1 to 6, characterized in that the monofunctional polyoxyalkylene ether d) ethylene oxide and propylene oxide units comprises.
8. A thermoplastic polyurethane according to claim 7, characterized in that the monofunctional polyoxyalkylene ether d) comprises at least 40 mol% of ethylene and up to 60 mol% of propylene oxide units.
9. Thermoplastic polyurethane according to any of claims 1 to 8, characterized in that the number average molecular weight of the monofunctional polyoxyalkylene ether d) 500 g / mol to 5000 g / mol, preferably 1000 g / mol to 4000 g / mol and particularly preferably 1000 to 3000 g / mol. Thermoplastic polyurethane according to any one of claims 1 to 9, characterized in that an additional catalyst e) is used in the reaction of components a) to d).
The thermoplastic polyurethane according to claim 10, characterized in that the catalyst e) is one or more compounds selected from the group of the tin-containing, bismuthaltiger, iron-containing, titanium-containing zirkoniumhaltiger or compounds and the tertiary amines.
A process for preparing a thermoplastic polyurethane according to any of claims 1 to 11 wherein the components a) to d) and optionally e) are mixed with each other directly, and optionally to a temperature in the range between 80 and 200 ° C and preferably between 100 and 180 ° C are heated.
A process for preparing a thermoplastic polyurethane according to any one of claims 1 to 1 1 wherein the components b) and d) are first reacted with component a) to form a prepolymer, which is then dissolved in an organic solvent, wherein the prepolymer is then reacted with the is brought dissolved in an organic solvent component c) to form the thermoplastic polyurethane to the reaction, wherein the component c) is especially a diamine.
A medical apparatus comprising a thermoplastic polyurethane according to any one of claims 1 to 11. 15. Medical device according to claim 14, characterized in that it consists of the thermoplastic polyurethane.
PCT/EP2012/066591 2011-08-29 2012-08-27 Hydrophilic thermoplastic polyurethanes and use thereof in medical equipment WO2013030148A1 (en)

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