Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
• • 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
  • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
  • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
  • A61L15/42—Use of materials characterised by their function or physical properties
  • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/089—Reaction retarding agents
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/487—Polyethers containing cyclic groups
  • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/675—Low-molecular-weight compounds
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
  • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • 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
  • C08G2210/00—Compositions for preparing hydrogels

Definitions

• the invention relates to hydrogels which are prepared from polyurethane (meth) acrylates in water with water-soluble redox initiators.
• Hydrogels are used for the medical treatment of wounds and are used in the form of appropriate wound dressings, especially where the moisturization of a wound leads to an improvement in wound healing (moist wound treatment).
• Synthetic polymers based on poly (meth) acrylates, polyvinylpyrrolidone or polyvinyl alcohol are typically used to prepare hydrogels. As a rule, such hydrogels are characterized by good compatibility with living tissue.
• hydrogels of polyurethanes which can be prepared by reaction of hydrophilic, isocyanate-functional prepolymers and a large excess of water, as described for example in EP-A 426 422, EP-A 455324, WO 9817215, WO 9913923 and WO2002060501.
• the large excess of water is necessary to avoid foaming by the liberated carbon dioxide, from the reaction of isocyanate groups with water.
• polyurethane hydrogels with a low content of initially added water (bubble-free) are not accessible.
• polyurethane hydrogels prepared in this way can only deliver water to a (dry) wound, whereas wound fluid can only be absorbed to a very limited extent.
• polyurethane hydrogels have hitherto also been a slow process in the prior art, in which often three components have to be used and in which the resulting gel still contains large amounts of unbound polyol.
• Aliphatic, isocyanate-functional prepolymers based on a polyethylene glycol, polypropylene glycol or glycerol as polyol in some cases in the presence of an accelerator, e.g. Oligoalkylenoxide with primary amino end groups used, i. that three components are necessary for faster-reacting systems.
• the polyol is used in significantly more than stoichiometric amounts. It follows that the hydrogels described still contain excess polyol and activator. Furthermore, the reaction times are very slow, so that the gel point is often reached only after 90 minutes. The extent to which such gels can be additized with antimicrobial substances has not been described hitherto.
• hydrogels are known which are prepared by free-radical crosslinking.
• GB-A 2086927 describes semi-IPN hydrogels which, initiated by peroxides, are at elevated temperature be prepared by crosslinking low molecular weight polyacrylates in the presence of an ethanolic solution of a linear polyurethane. Subsequently, the Hüfsatessstoff ethanol is removed.
• GB-A 2131442 describes low molecular weight polyallyl compounds and in GB 2150938 hydroxyethyl methacrylate and other monoacrylates as external free-radically polymerizing monomers. Again, an auxiliary solvent such as ethanol and peroxides were used at elevated temperature.
• EP-A 351 364 describes hydrogels which are prepared from N, N-dimethylacrylamide, fluorine-containing polymers and crosslinkers, it also being possible to use unsaturated isocyanates such as MOI (methacryloyloxyethyl isocyanate) or TMI ( ⁇ , ⁇ -dimethyl-3-). Isopropenyl benzyl isocyanate) reacted polyols, such as polyvinyl alcohol or triethylene glycol can be used as a crosslinker.
• Crosslinking was by initiation with UV or radical initiators. The same disadvantages apply as described above. Also, UV crosslinking is critical in body contact (reaction with the skin, eye protection of the patient and the medical staff).
• hydrogels prepared via redox polymerization which are prepared from polyvinyl alcohol and a crosslinking agent prepared from FEMA et al, Polymer, (1998) 39 (10), 1977-1982 from HEMA and glycolide.
• polyurethane hydrogel which can be prepared using only small amounts of water as needed and thus can additionally absorb wound fluid in contact with a wound.
• the polyurethane hydrogel should continue to deliver water to (dry) wounds. Since the polyurethane hydrogel may need to be formed first in a wound or other body orifice (e.g., in endoscopic procedures), crosslinking must be without substantial exotherm. The use of radiation curing (for example UV crosslinking) should be avoided due to the high expense. All liquid precursors as well as the polyurethane hydrogel itself should have a good biocompatibility, this should be dispensed with the use of organic solvents.
• aqueous solutions of hydrophilic polyurethane acrylates having molar masses of at least 2000 g / mol can be crosslinked by a redox system at temperatures of 10 to 42 ° C, wherein the water content of the produced polyurethane hydrogel can be adjusted within wide limits.
• the use of organic solvents or monomeric acrylates is not necessary; the resulting polyurethane hydrogels show good biocompatibility.
• the invention therefore relates to a process for the preparation of polyurethane hydrogels, in which
• Reducing agent wherein the oxidizing agent from the redox potential is capable of reacting with the water-soluble reducing agent to form a radical
• the hydrogels thus obtainable are also an object of the invention.
• hydrophilic polyurethanes having olefinically unsaturated groups essential to the invention are obtainable by reacting polyisocyanates with hydroxy-functional polyalkylene oxides.
• polyalkylene oxides preferably have an ethylene oxide content of at least 50%, based on the oxalkylene units present, particularly preferably at least 60%. Unless otherwise stated, all percentages are by weight (here and below).
• these polyalkylene oxides are copolymers of ethylene oxide and propylene oxide having an ethylene oxide content of 50 to 100%, preferably 60 to 82%, started on polyols or amines, such as water (considered as a diol), ethylene glycol, propylene glycol , Butylene glycol, glycerol, TMP, sorbitol, pentaerythritol, triethanolamine, ammonia or ethylenediamine.
• polyols or amines such as water (considered as a diol), ethylene glycol, propylene glycol , Butylene glycol, glycerol, TMP, sorbitol, pentaerythritol, triethanolamine, ammonia or ethylenediamine.
• the OH functionality is preferably 2 to 6, particularly preferably 3 to 6, very particularly preferably 3 to 4.
• olefinically unsaturated isocyanates such as MOI (methacrylic acid isocyanatoethyl esters, TMI (3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate) or allyl isocyanate.
• a prepolymer is prepared by reacting a 1.6 to 30-fold equivalent amount of diisocyanate based on the OH groups of the polyalkylene oxide.
• the NCO / OH ratio is preferably 4: 1 to 12: 1, more preferably 2: 1.
• catalysts such as amines or tin compounds and / or stabilizers such as benzoyl chloride, isophthaloyl chloride, dibutyl phosphate, 3-chloropropionic acid or methyl tosylate may be added during the preparation.
• the reaction temperature is from 20 to 120 ° C., preferably from 60 to 100 ° C.
• Excess unreacted isocyanate can then be removed, preferably by means of thin film distillation.
• Suitable saturated diisocyanates correspond to the general formula (I)
• R is a C 4 -C 22 -alkylene radical, a C 3 -C 22 -cycloalkylene radical, a C 8 -C 22 -aralkylene radical in which the carbon atoms linked to the isocyanate group are sp 3 -hybridized, or a C 6 -C 18 -aryl radical stands.
• diisocyanates examples include HDI, IPDI, bisisocyanatocyclohexylmethane, 2,2,4-trimethylhexamethylene diisocyanate, bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyciodecane, xylylene diisocyanate, tetramethylxylylene diisocyanate, norbornane diisocyanate, cyclohexane diisocyanate, diisocyanatododecane, 2,4-TDI, 2,6-TDI, 2 , 2-, 2,4- or 4,4-MDI, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 3,4'-diisocyanatodiphenyl ether, 1,5-naphthylene diisocyanate or mixtures thereof.
• the aliphatic diisocyanates of the abovementioned type are preferred because of the extensive toxicological safety of the hydrolysis products of the polyurethanes resulting from them.
• the isocyanate-functional prepolymers obtained in this way are reacted with compounds which, in addition to the unsaturated group, have at least one isocyanate-reactive group.
• Preferred isocyanate-reactive groups are amino or hydroxy functions, preferably hydroxy functions.
• the equivalent ratio of NCO groups to NCO-reactive groups is preferably 1.5: 1 to 1.0: 1.
• An excess of NCO-reactive groups should be avoided, since otherwise unsaturated monomers remain. With a deficit of such compounds remaining free NCO groups are removed by reaction with water or monools such as methanol, ethanol or isopropanol before application.
• hydrophilic polyurethanes having olefinically unsaturated groups takes place at temperatures of 20 to 80 0 C, preferably in the presence of polymerization inhibitors such as hydroquinone, Hydrochinonmonoalkylethern, di-tert-butyl cresol or methylene-bis- (tert-butyl cresol) and of catalysts the OH-NCO reaction, such as tin compounds or amines.
• polymerization inhibitors such as hydroquinone, Hydrochinonmonoalkylethern, di-tert-butyl cresol or methylene-bis- (tert-butyl cresol)
• catalysts the OH-NCO reaction such as tin compounds or amines.
• Water-soluble oxidizing agents are substances which are capable of oxidizing the substances listed under water-soluble reducing agents or other substances to form free radicals.
• Water-soluble oxidizing agents which can be used are hydrogen peroxide and its inorganic salts, peroxides, hydroperoxides, such as tert-butyl hydroperoxide, percarboxylic acids, such as peracetic acid, perbenzoic acid, per-m-chlorobenzoic acid, phthalic monoperacid, and their ammonium, alkali or alkaline earth salts, inorganic peracids, preferably in the form of their ammonium or alkali salts, such as perboric acid, percarbonic acid, peroxodisulphuric acid, peroxodiphosphoric acid, Caro's acid, periodic acid, permanganic acid, perrhenic acid, halogens or halogenated substances, hypohalides, sodium chlorite, cerium (IV) compounds, such as cerium ammonium nitrate, or metal ions a higher oxidation state than the water-stable ones, such as vanadium (V) compounds, manganese (
• Water-soluble reducing agents are substances which are capable of reducing the substances mentioned under water-soluble oxidizing agents to form free radicals.
• water-soluble reducing agents may be ascorbic acid, isoascorbic acid, compounds containing vicinal OH-Gnippen, such as glycerol or sugar alcohols or sugars or oligo- or polysaccharides, reducing sugars, such as glucose, formaldehyde, glyoxal, glyoxylic acid, sodium sulfite, ammonium sulfite, potassium sulfite or the corresponding bisulfites or bisulfates or metabisulfites, sulfite-aldehyde adducts, sodium thiosulfate, potassium thiosulfate, thiourea, hydroquinone, pyrogallol, gallic acid, oxalic acid and its salts, tartaric acid and its salts, malonic acid and its salts, formic acid
• activators may also be used.
• Preferred activators are transition metal salts which, like iron, can change their oxidation state in odd steps.
• Particularly preferred activators are iron salts.
• iron salts are iron (II) or iron (HT) salts, such as iron (II) chloride, ammonium iron (E) sulfate, iron (II) sulfate, iron (M) sulfate, iron (IH) chloride, iron (m) nitrate, iron (II) acetylacetonate, potassium or sodium or ammonium hexacyanoQO 2 -ferrat, potassium or sodium or ammonium hexacyano (III) ferrate, sodium nitroprussiate, ferrous D-gluconate, iron (II) lactate, iron (II) iodide, iron (II) perchlorate, iron (III) perchlorate, iron (II) tetrafluoroborate or iron (III) tosylate, wherein in addition complex ligands, such as nitrilotriacetic acid or EDTA can be added.
• complex ligands such as nitrilo
• A) 1.0 part by weight of the hydrophilic, unsaturated polyurethane, in B) 0.2 to 19 parts by weight of water and in C) as a redox system in each case based on the sum of the amounts of A) and B. ) 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-% of the water-soluble oxidizing or reducing agent used.
• an activator is used, it is added in amounts of from 0.00001 to 0.01% by weight, preferably from 0.0001 to 0.001% by weight of transition metal salt, based on the sum of the amounts of A) and B).
• the procedure is preferably such that the oxidation agent and the reducing agent are each provided separately from one another as an aqueous solution.
• the hydrophilic polyurethane to be crosslinked is dispersed or solved.
• the crosslinking is initiated by combining both solutions, if appropriate with the addition of an activator which may be dissolved.
• both the solution of the oxidizing agent and that of the reducing agent contains hydrophilic polyurethane in dissolved or dispersed form.
• the Hydrogel is preferably 5 to 100 0 C, particularly preferably from 10 ° to 42 ° C.
• antibiotically active substances may also be added, as described in WO 2002060501, water-soluble substances being preferred. It is important to note the possible interaction of these substances with the oxidizing or reducing agents, whereby a mutual destruction of the components is possible, which makes a long-term storage before application impossible.
• antibiotically active substances may also take over the role of all or part of oxidizing or reducing agents, such as peroxodisulfates, hydrogen peroxide, permanganates, silver (I) compounds, sulfites or aldehydes.
• thickeners such as polyvinyl alcohol, methyl, hydroxyethyl, hydroxypropyl or carboxymethyl ethers of polysaccharides, such as cellulose or starch, polyvinylpyrrolidone, polyacrylic acid, methylvinyl ether-MSA copolymers, inorganic thickeners, such as silicic acids, aluminosilicates or aluminum hydroxides, Polypeptides, polysaccharides such as gum arabic or agar, chitosan, hyaluronic acid or polyurethane thickener, wherein the thickeners can also take over the role of reducing agents wholly or partially.
• the thickeners can be introduced in advance into the aqueous solutions of the hydrophilic urethane acrylate or can be added only shortly before the reaction.
• polyurethane hydrogels of the invention are useful e.g. as wound dressings.
• the polyurethane hydrogels can be formed either directly by crosslinking one or more of the above-described component (s) on the skin or wound, or the use of a previously prepared polyurethane hydrogel, typically in the form of a flat wound dressing.
• the polyurethane hydrogels according to the invention are furthermore suitable as an adhesion barrier which prevents the unwanted coalescence of organs ("post-surgical adhesion prevention,
• the polyurethane hydrogel is prepared from one or more initially liquid component (s) and can thus be metered into the body, in particular during endoscopic procedures through the described networking.
• the polyurethane hydrogel prepared therefrom may be biostable or biodegradable. Especially when used as PSA, the use of a biodegradable polyurethane hydrogel is preferred.
• the application is possible in humans or in animals.
• 112g of a hexafunctional sorbitol-launched polyethylene oxide having a molecular weight of 6740 g / mol was added with 0.1 g BKF and 0.1 g DBTL and added 15 g MOI. It was allowed to stand at room temperature for 7 days.
• Prepolymers were mixed with 0.1 g BKF, 0.1 g DBTL and 6.5 g hydroxyethyl methacrylate (HEMA).

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Hematology (AREA)
• Materials Engineering (AREA)
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• Life Sciences & Earth Sciences (AREA)
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• Materials For Medical Uses (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2007
  • 2007-01-18 DE DE102007002783A patent/DE102007002783A1/de not_active Withdrawn
• 2008
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  • 2008-01-08 KR KR1020097014948A patent/KR20090104826A/ko not_active Withdrawn
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  • 2008-01-08 CA CA002675605A patent/CA2675605A1/en not_active Abandoned
  • 2008-01-08 RU RU2009131140/04A patent/RU2009131140A/ru not_active Application Discontinuation
  • 2008-01-08 WO PCT/EP2008/000065 patent/WO2008086954A1/de not_active Ceased
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