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    • 专利摘要:
    An antimicrobial agent for the biocidal equipping of biocide-based polymers is described, whose molecules have at least one nitrogen atom with a lone pair of electrons. In order to achieve a high degree of insolubility without loss of the biocidal effect, it is proposed that the biocide is coordinately bonded to a metal complex via the lone pair of electrons of the nitrogen atom.
    公开号:AT516549A1
    申请号:T50844/2014
    申请日:2014-11-20
    公开日:2016-06-15
    发明作者:
    申请人:Wenatex Forschung - Entw - Produktion Gmbh；
    IPC主号:
    专利说明:

    (40051) II
    The invention relates to an antimicrobial agent for the biocidal equipping of polymers based on biocides, whose molecules have at least one nitrogen atom with a lone pair of electrons.
    In the biocidal equipping of polymers, in particular of polyurethane foams or of polymer fibers used in the textile industry on the basis of polyethylene terephthalate (PET), polyacrylonitrile (PAN), polypropylene (PP) and the like., The aim is to intervene on the one hand in the metabolism of microorganisms and on the other to deprive the microorganisms of the food base. The biocides most effective for this purpose have a molecular weight well below 1000, which generally supports the volatility, solubility and migration of these agents. In order to avoid environmental pollution by such biocides, it is known (EP 2 420 521 A1, EP 2 505 059 A1) to increase the molecular weight by polymerizing the active compounds or by attaching to polymers and to strive for covalent binding of the active compounds to the polymer matrix , For example, a series of biocides with effective primary and secondary amines or with reactive hydroxyl groups in the molecule can be successfully incorporated into a polyurethane or epoxy resin matrix. However, the most effective biocides often contain only tertiary nitrogen, no (sufficiently reactive) Hydroxlgruppen or secondary amino groups, which are so inert that they react only subordinate with the polyaddition, so that the polyaddition has priority over the covalent bond.
    In addition, often the most effective base molecules in covalently bound form lose their excellent action because they must retain some mobility (solubility) to develop this biological effect.
    The invention is therefore based on the object of specifying an antimicrobial agent which, despite a good solubility of its Biocidmoleküle in water environmental pollution by the Biocidmoleküle largely excludes in a long-term effect, without having to accept restrictions on the biocidal effect in purchasing.
    Based on an antimicrobial agent of the type described above, the invention solves the stated object in that the biocide is coordinatively bonded to a metal complex via the lone pair of electrons of the nitrogen atom.
    It has surprisingly been found that antimicrobial agents in which the biocide is coordinately bound to a metal complex are generally not water-soluble, but retain the antimicrobial effect of the biocide, although the biocide molecules are considered to be non-volatile. This is attributed to the coordination bond, which allows sufficient mobility of the biocide molecules permanently bound to the metal complex in order to maintain interaction with the surface of the microorganisms to be controlled.
    Imidazoles, benzimidazoles, oxazoles, isoxazoles, oxadiazoles, biguanides, thiazoles, isothiazoles, pyrimidines and pyridines have proved to be advantageous biocides in this context. As metal complexes are in particular phthalocyanine with copper, zinc, tin, iron or cobalt as the central atom, porphyrins with magnesium, copper or iron as the central atom or corrole with copper, zinc, iron, gold, silver, vanadium, molybdenum or cobalt as the central atom in Question. Due to the different coordination numbers 2,4 and 6 of the central atoms, several nitrogen-containing biocide molecules or biocide molecules can be docked several times, depending on the type of metallic central atoms of the metal complexes, resulting in different binding possibilities in terms of quantity and stability.
    When using a phthalocyanine with copper as the central atom, the planar arrangement of the ligands, which is possible owing to the coordination number 4 of the copper, can be advantageously used to coordinate larger biocide molecules with sufficient mobility. Biguanides are particularly suitable for this purpose, it being possible in each case for the copper atom to be bonded to one nitrogen atom of two biguanide molecules, but only one biguanide molecule is ordinarily bound coordinately to the central copper atom in order to use particularly stable conditions.
    As the biguanide, a polyaminopropyl biguanide (molecular weight Mr = 800-10,000) having the structural formula is advantageously suitable
    where n = 5-50, a polyhexamethylene biguanide (Mr = 800-10,000) having the structural formula
    where n = 5-50 and a polyoxyalkylene biguanide (Mr = 1000-15000) having the structural formula
    where: m = 2 -10 and n = 5 - 50.
    Porphyrins, such as chlorophylls, with magnesium or copper as the central atom show steric reasons, a pronounced affinity for imidazoles, benzimidazoles and nitrogen-sulfur compounds.
    By way of example, in this context, an imidazole having the structural formula
    where R = hydrogen, an alkyl or a halogen, or a benzimidazole of the structural formula
    be specified. The same applies to corrole, in particular cobalamin with cobalt as the central atom.
    Porphyrins with iron as the central atom, z. As hemines, can with a low molecular weight biguanide, preferably a hexamethylene bis (p-chlorophenyl) biguanide the structural formula
    but also with oxygen-nitrogen heterocycles, such as an isothiazole of the structural formula
    an isoxazole of structural formula
    where R = hydrogen, an alkyl or a halogen, or an oxadiazole having the structural formula
    be bound coordinatively. In this connection, a biocide based on oxygen, nitrogen and sulfur, in particular a 2-mercaptopyridine-N-oxide having the structural formula
    be used advantageously.
    The following examples are intended to illustrate the invention, which show biocidal activity and its stability against migration and leaching, but does not restrict the subject of the invention.
    Example 1:
    Phthalocyanine with copper as the central atom (CuPhthC) occurs in a total of 11 stereospecific configurations, of which the a, ß and ε variants are used industrially. They are visually distinguished by different shades of blue: α reddish blue, thermally unstable β greenish blue, highly thermally stable ε strongly reddish blue, chemically unstable, ie more reactive than α and β, so that according to the invention only the ε variant is used. 57.6 g (0.1 mol) of CuPhthC are suspended in 200 ml of dimethylformamide (DMF) and heated (60 ° C) with 1300 g (0.1 mol) of polyhexamethylene biguanide (polyhexanide), M.R. = 1298 , dissolved in 1800 ml of H 2 O, and stirred for 2 hours. The color loses very quickly the reddish part, the suspension is much more viscous.
    After filtration and drying of the product obtained, 1216 g of the coordination compound gave 1 mol of CuPhthC + 1 mol of polyhexanide as the azure dye.
    Example 2: 73 g (0.1 mol) of a copper-containing chlorophyllin (CuChloroph) which is obtainable in the flandel as E141 - natural green (= food coloring matter) were partly dissolved in 250 ml of water, partly suspended and mixed with 20.3 g (0.1 mol ) 2- (4-thiazolyl) benzimidazole ("thiobendazole") and the green suspension stirred for 30 minutes at room temperature. The hue became much more intense and yellowish. After isolation, 85.4 g of the coordination compound 1 mol of CuChloroph + 1 mol of thiobendazole were obtained as a green-yellow dye.
    Example 3: 67 g (1 mol) of pyrrole were treated with 92 g (1 mol) of 4-methylbenzaldehyde in 400 ml of methanol + 20 ml of conc. Refluxed FICL under a nitrogen atmosphere for 1 hour, spontaneously forming a dark blue solution of tetratolylporphyrin. After addition of 136 g (1 mol) of zinc chloride, a suspension of the porphyrin-zinc complex was formed. Then 282 g of 4,5-dichloro-2-octylisothiazolone (DCOIT) were added and after a 1 hour stirring phase, the formed, deep blue coordination compound was filtered off with suction. After drying, 310 g of tetratolylporphyin / Zn / DCOIT coordination compound were obtained.
    Example 4: 6.52 g (0.01 mol) of hemin were dissolved in 250 ml of distilled H 2 O and admixed with 1.5 g (0.01 mol) of 2-pyridinethiol-1-oxide (pyrithione), sodium salt, whereupon a reddish brown Precipitation of the expected coordination compound 1 mol of hemin + 1 mol of pyrithione occurred. After customary isolation, 7.4 g of the desired product were obtained.
    The following examples are intended to show the biocidal effect when incorporated into a polyurethane foam.
    Example 5: 95 g of a trifunctional polypropylene glycol (OH number: 46), 3.4 g of H 2 O, 2.0 g of a silicone stabilizer based on a polysiloxane-polyethylene glycol copolymer and 1.5 g of 1,4-diazabicyclo [2.2.2] octane ( DABCO) as a foam catalyst, dissolved in 3 g of tripropylene glycol, are intensively mixed with 65 g of diphenylmethane diisocyanate (MDI) having an NCO content of 29.5% corresponding to NCO Index 103% and within about 60 seconds to an elastic foam with a Density RG = 45 kg / m3 foamed. Part of this foam serves as a comparative sample (zero pattern).
    Example 6:
    Analogously to Example 5, but with a total of 170 g based 5% additive (= 0.85 g) polyhexanide, Mr = 1300. The resulting foam had a density RG = 46 kg / m3.
    Example 7:
    Analogously to Example 5, but with a total weight-related addition of 0.3% = 0.50 g of thiabendazole. The foam obtained had a density RG = 45 kg / m3.
    Example 8:
    As Example 5, but with an addition of 0.45% of a CuPhtC / polyhexanide complex (corresponding to 0.5% polyhexanide) from Example 1.
    Example 9:
    Analogously to Example 5, but with an addition of 1.8% of a coordination complex from Example 2 (corresponding to 0.4% thiabendazole).
    Example 10: 105 g of the polyol mixture It. Example 5 are thoroughly mixed with 0.05 g of ε-copper phthalocyanine and 0.6 g Polyhexanidchlorwasserstoff and after a waiting time of 15 minutes with 65 g of methylene diphenyl diisocyanate (MDI) analogously to Example 5 and foamed. The resulting foam had a density RG = 46 kg / m3.
    Test of the biocidal effect
    Samples were prepared from the foams according to Examples 5 to 10 under otherwise identical conditions and the antimicrobial activity was determined according to the Japanese industrial standard JIS Z 2801: 2000 by determining the reduction factor IR for Escherichia coli (Gram positive) and Staphylococcus aureus (Gram negative) after a week period , The results are summarized in the table below. The values of the original sample are compared with those of the samples after three washings in water at a temperature of 60 ° C (not eluted / eluted).
    The low biocidal effect of the blank (number 5) is based on the content of the tertiary catalyst used. Amines returned before the eluation.
    The comparison of the reduction factor IR of the inventive samples Nos. 8 to 10 with that of the comparative samples according to the prior art shows on the one hand the excellent biocidal effect and on the other hand the good stability and insolubility of the coordinate compounds, which in part probably also on the chemical integration into the polyurethane matrix must be returned.
    The examples were carried out with soft polyurethane foam, but of course are not restricted to cellular bodies, nor to polyurethane. Epoxy formulations for metal coatings achieved comparable results.
    When used in thermoplastics, of course, in situ synthesis (It Example 10) can not be used because of the absence of a temporary solvent. In this case, isolated coordination compounds (according to Examples 1 to 4) can be used, wherein in advance the thermal stability (processing temperature usually> 150 - 250 ° C) is to be checked. In contrast, the processing temperature for the mentioned polyaddition plastics is moderate at 25-80 ° C.
    权利要求:
    Claims (7)
    [1]
    Patent Attorneys Dipl.-Ing. Helmut Hübscher Dipl.-Ing. Karl Winfried Hellmich Spittelwiese 4, 4020 Linz (40051) II Claims
    1. Antimicrobial agent for biocidal equipping polymers based on biocides whose molecules have at least one nitrogen atom with a lone pair of electrons, characterized in that the biocide is coordinated via the lone pair of nitrogen atom to a metal complex.
    [2]
    2. Antimicrobial agent according to claim 1, characterized in that the biocide is an imidazole, benzimidazole, oxazole, isoxazole, oxadiazole, biguanide, thiazole, isothiazole, pyrimidine or a pyridine.
    [3]
    3. Antimicrobial agent according to claim 1 or 2, characterized in that the metal complex is a phthalocyanine with copper, zinc, tin, iron or cobalt as the central atom, porphyrin with magnesium, copper or iron as the central atom or a corrole with copper, zinc, iron, Gold, silver, vanadium, molybdenum or cobalt as the central atom.
    [4]
    4. Antimicrobial agent according to claims 2 and 3, characterized in that a phthalocyanine with copper as the central atom with a polyaminopropyl biguanide, a Polyhexamethylenbiguanid or a Polyoxyalkylenbiguanid is coordinately bonded.
    [5]
    5. Antimicrobial agent according to claims 2 and 3, characterized in that a porphyrin is coordinated with magnesium or copper as the central atom coordinately with an imidazole or a benzimidazole.
    [6]
    6. Antimicrobial agent according to claims 2 and 3, characterized in that a porphyrin with iron as the central atom with a hexamethylene bis (p-chlorophenyl) biguanide, an oxazole, isoxazole or oxadiazole or a 2-mercapto-topyridine nitrogen oxide is coordinately bonded.
    [7]
    7. workpiece of a polymer, in particular of a foam, characterized in that the workpiece is equipped with an antimicrobial agent according to one of claims 1 to 6. Linz, November 20, 2014 Wenatex Research - Development - Production GmbH by: / Dl Helmut Hübscher / (electronically signed)
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    引用文献:
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    法律状态:
    优先权:
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    EP15808077.0A| EP3220740A1|2014-11-20|2015-11-20|Antimicrobial agent for the biocidal finish of polymers|
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