• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    A contact biocide is described according to the formula wherein A is a fragment that coordinates as a cation to the lone pair of electrons of a nitrogen atom, B a fragment that reacts as an anion with a carbocation to form an uncharged product, R is an organic residue from a saturated aliphatic chain C6 to C30 is a saturated cycloaliphatic radical, a monounsaturated or polyunsaturated aliphatic chain having at least 6 carbon atoms, an oligooxazolines crosslinking agent, an aryl spacer to cross-linking oligooxazolines, a phenyl, an alkylphenyl, a heteroaryl or copolymers thereof and X is a biocidally inactive anion and where (n + m)> 10.
    公开号:AT511386A1
    申请号:T6202011
    申请日:2011-05-03
    公开日:2012-11-15
    发明作者:
    申请人:Ke Kelit Kunststoffwerk Gmbh；
    IPC主号:
    专利说明:

    (37877) Ιί
    The invention relates to contact biocides.
    In order to intervene in metabolic processes that are characteristic of unicellular organisms, biocides, such as sulfonamides, cephalosporins, tetracyclines and the like, have a small molecular structure and are therefore usually water-soluble. However, it is disadvantageous that it is also possible to influence other metabolic processes that take place in an aqueous medium. By contact biocides, these disadvantages can be avoided. Contact biocides usually form high molecular weight, protonatable chemical compounds that kill the protozoa by mere contact due to static charges and the resulting cell lysis, without going into aqueous solution or intervene in the internal metabolism. However, the known contact biocides, for example, polymers of basic methacrylates, due to the system-immanent ester groups in practice could not prevail, because the ester groups do not have sufficient stability to hydrolysis and tolerate only limited with the market-dominant groups of polyolefins.
    In order to specify suitable contact biocides, polymers obtained by cationic polymerization of a 2-oxazoline have already been tested for their antibacterial activity. Here, 2-ethyl-2-oxazoline was subjected with methyltosilicate as a catalyst of a ring-opening polymerization, which led to poly (2-ethyl-2-oxazoline). Such a quaternary ammonium functionalized poly (2-ethyl-2-oxazoline) had antimicrobial activity against S. aureus, which could be improved when the quaternary ammonium salt and corresponding functional groups on the polymer end aggregated in a unimolecular micelle. The subsequent joint attack of both groups on a phospholipid membrane led to the perforation of the membrane. However, this antimicrobial poly (2-ethyl-2-oxazoline) is water-soluble. Kkkk · kt · kk · · · ikk kikk k ·· # «kt · k · k ·« * «· ·· * ··· kk «2
    For the preparation of water-insoluble antimicrobial surfaces, a block copolymer of poly (2-methyl-2-oxazoline) has already been proposed as a hydrophilic block with quaternary nitrogen as an end group. In addition, it is known to copolymerize a poly (2-oxazoline) which on the one hand had polymerizable end groups but on the other hand has a quaternary nitrogen end group with hydroxyethyl methacrylate and glycerol dimethacrylate, thereby forming a polymer network. However, these known contact biocides take no account of the amphiphilia of a cytoplasmic membrane, which requires a sensitive coordination between the hydrophilicity and hydrophobicity of the contact biocide for improved antibacterial effect.
    Finally, it is known to convert the poly (2-ethyl-2-oxazoline) obtained by a ring-opening polymerization by acid-catalyzed hydrolysis to linear polyethyleneimine (polyaziridine). Copolymers can be used to obtain amphiphilic systems which are used, for example, as micellar catalysts, nonionic surfactants or hydrogels. An antimicrobial effect could not be observed, however, because of the non protonizable amide structures.
    The invention is therefore based on the object to optimize the known antibacterial properties of poly (2-oxazolines). In addition, a process for the simple technical production of contact biocides according to the invention should be specified.
    The invention solves the problem by a contact biocide according to the formula
    B Jm n
    A is a fragment which coordinates as a cation to the lone pair of electrons of a nitrogen atom, B a fragment which reacts as an anion with a carbocation to form an uncharged product, R an organic radical of a saturated aliphatic chain C6 to C30, a saturated cycloaliphatic Radical, a mono- or polyunsaturated aliphatic chain having at least 6 carbon atoms, an oligooxazolines crosslinking agent, an aryl spacer to cross-linking oligooxazolines, a phenyl, an alkylphenyl, heteroaryl or a copolymer thereof and X is a biocidally inactive anion and wherein (n + m )> 10.
    Due to the coordinated amide and amine components of the contact biocides according to the invention, the amphiphilia of the cytoplasmic membranes can be taken into account in an advantageous manner because the amide content has a significant influence on the lipophilicity and the amine content on the hydrophilicity of the contact biocide. Due to a corresponding coordination of the amide and amine contents, it becomes possible to provide the hydrophilicity required for lysis of the lipid-dominated bacterial envelopes with a pronounced lipophilicity, despite only slight water solubility.
    As fragment A is preferably hydrogen, an alkyl Ci to Ce or a benzyl group. As fragment B can advantageously be used a hydroxy group or an amino group.
    The organic radical R is intended to prevent water solubility of the amide moiety and therefore preferably forms longer chains, the required chain length depending on the mobility of the chain molecules. For example, saturated aliphatic chains require at least 6 carbon atoms for this purpose, and the desired effect can be assisted by substitution with a mercapto, hydroxy or amino group. Preference is given to chains having 9 to 18 carbon atoms.
    If a saturated cycloaliphatic radical R is used, the number of carbon atoms can be reduced because of the lower molecular mobility. It is therefore possible to use a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl which is optionally substituted by a mercapto or a hydroxy group. Even lower molecular mobility is achieved by mono- or polyunsaturated aliphatic chains. Starting materials for such intermediates are advantageously available as unsaturated fatty acids of biological origin.
    The at least substantial insolubility of the amide portion in water can also be achieved by an alkyl spacer to be crosslinked oligooxazolines or an aryl spacer to cross-linking oligooxazolines.
    With phenyl as the radical R which is optionally substituted by a hydroxy, amino, nitro, halogen, alkyl, and / or trifluoromethyl group, the basicity of the amide group and thus also the water solubility can be influenced. The same applies to the use of a heteroaryl as the radical R, where preferably a pyridyl, a thienyl, a thiazolyl, a triazolyl, a pyrimidinyl or a thiadiazolyl find use.
    The anion bound to the nitrogen cation of the amine group can be chosen differently. As preferred examples, a chloride, a hydrogen sulfate, a sulfate, a dihydrogen phosphate, a hydrogen phosphate, a phosphate, a nitrate, a bicarbonate, a carbonate and an alkanoate anion can be given.
    Of course, the invention is not limited to polymers with chloride as counterion. Instead of hydrolysis with hydrogen chloride, another hydrolysis medium can be used, for example sulfuric acid. But it can also be a subsequent protonation of a nitrate, phosphate, carbonate or the like. Be made. In addition, hydrolysis can be carried out by means of organic mono-, di- or polycarboxylic acids as eonate. # * m * «« «« «« «« «« «♦ · · I • #« φ »φ φ φ φ · φ f · φ» 4 φ «V φ φ Φ * Φ Φ Φ 9 1« «» · · 9
    For the preparation of contact biocides according to the invention, a 2-oxazoline can be used in a simple manner, which is first polymerized in a cationic ring-opening manner before the polymer obtained is subjected to partial hydrolysis. Although a hydrogen chloride is suitable for the hydrolysis, the invention is of course not limited to this hydrolysis medium. Due to the partial hydrolysis of the poly (2-oxazoline), its amide content is partly converted into an amine fraction which can be adjusted by the degree of hydrolysis, thus opening up a simple possibility for the mutual coordination of the hydrophobicity and the hydrophilicity. Because of the rest of the R invention caused by the longer chains results in a temporal hydrolysis that allows compliance with a given degree of hydrolysis in a simple manner. The reaction rate is only dependent on the particular concentration of amide. The degree of hydrolysis is proportional to the water solubility of the contact biocide, the water solubility of which can thus also be adjusted via the degree of hydrolysis. At a degree of hydrolysis of about 10% shows an antibacterial activity, which increases with increasing hydrolysis, the preferred degree of hydrolysis is 20 to 75%, because at such a degree of hydrolysis, the water solubility at a suitable radical R of the amide generally plays no role.
    The amine portion of the contact biocide according to the invention can be incorporated to increase the water insolubility in the polymer matrix. For this purpose, the nitrogen atoms can be ionically bonded by means of polymeric or copolymeric carboxylic acids, for example poly [ropylene-co-methacrylic or maleic acid]. Another possibility is a partial addition reaction of the nitrogen atoms on polymeric epoxide structures, such as poly (bis-phenol glycidyl ether) or polyolefin-co-glycidyl methacrylate. However, it is also possible cross-linking, with the help of small proportions (0.5 to 10 wt.%) Of polyfunctional 2-oxazolines during the ring-opening polymerization. As aryl spacers in this context can advantageously phenylene-1,3-bis-2-oxazoline and phenyl-1,3,5-tris-2-oxazoline and as alkyl spacer tetramethylene-1,4-bis-2-oxazoline and octamethylene-1 , 8-bis-2 oxazoline be used. In addition, substitutes can be • • • • »• • • *« ··· «· · · * *« · · · *. Embedded in the polymer matrix which are available for the reaction on the organic radical of the amide moiety. Suitable for this are ester. Amide, urethane, thio-click bonds or oxirane additions.
    Example:
    For the synthesis of poly (2-nonyl-2-oxazoline), a stock solution of 2-nonyl-2-oxazoline (15.06 g, 76.1 mmol), methyl tosylate (0.236 g, 1.27 mmol) and acetonitrile (38 ml) under protective gas. In each case, 15 ml of the stock solution were transferred to a microwave vessel, this sealed and polymerized at 150 ° C for 16 minutes. The polymer was then filtered off, washed with acetonitrile and dried in vacuo.
    Yield: 94% white solid
    The poly (2-nonyl-2-oxazoline) thus obtained (0.500 g, 2.53 mmol) was weighed into a microwave vial, added with 6 M HCl (2 mL, 0.01 mol), and kept in the microwave for different times Hydrolyzed to 160 ° C. The resulting light yellow solid, poly (2-nonyl-2-oxazoline-co- (aziridinium chloride), was washed with 5 ml of acetone, the product was filtered off and dried in vacuo The degree of hydrolysis can be taken from the table below depending on the reaction time.
    Reaction time (min) 5 10 20 25 30 35 40 45 Degree of hydrolysis (%) 24 41 62 71 75 81 86 87
    The contact biocide according to the invention obtained with a degree of hydrolysis of 75% was kneaded in an amount of 1% by weight into a polypropylene having a melt flow index MFR of 0.42 at a temperature between 170 and 180 ° C. and from the homogeneous polymer mass sample platelets of 60 × 60 x 2 mm sprayed. These coupons were tested against E. coli, S. aureus and Listeria monocytogenes according to JIS Z 2801: 2000. Compared with all Gram-positive and Gram-negative bacteria mentioned, an inhibition of more than 99.9% was achieved. This value remained the same even after a one-week storage of the test slides in distilled water.
    • W s
    权利要求:
    Claims (12)
    [1]
    Patent Attorneys Dipl.-Ing. Helmut Hübscher Dipl.-Ing. Karl Winfried Hellmich Spittelwiese 7, A 4020 Linz (37877) II Claims: 1. Contact biocide according to the formula

    wherein A is a fragment that coordinates as a cation to the lone pair of electrons of a nitrogen atom, B a fragment that reacts as an anion with a carbocation to form an uncharged product, R is an organic radical of a saturated aliphatic chain Cö to C30, a saturated cycloaliphatic radical , a mono- or polyunsaturated aliphatic chain having at least 6 carbon atoms, an oligooxazolines to be crosslinked, an aryl spacer to cross-linking oligooxazolines, a phenyl, an alkylphenyl, a heteroaryl or copolymers thereof, and X is a biocidally-inactive anion and where (n + m) > 10.
    [2]
    2. Kontaktbijzid according to claim 1, characterized in that the fragment A is hydrogen, an alkyl Ci to Cö or a benzyl group.
    [3]
    3. Kontaktbijzid according to claim 1 or 2, characterized in that the fragment B is a hydroxy group or an amino group. 2 * · 4 * · · · ·
    [4]
    4. Kontaktbijzid according to any one of claims 1 to 3, characterized in that the organic radical R is a saturated aliphatic chain Cg to Cie.
    [5]
    5. Kontaktbijzid according to any one of claims 1 to 3, characterized in that the organic radical R is a mono- or polyunsaturated aliphatic chain of C8 to C25
    [6]
    6. Kontaktbijzid according to any one of claims 1 to 3, characterized in that the cycloaliphatic ring of the organic radical R is a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
    [7]
    7. Kontaktbijzid according to any one of claims 1 to 3, characterized in that the organic radical R as Alkyiphenyl has a benzyl.
    [8]
    8. Kontaktbijzid according to any one of claims 1 to 3, characterized in that the organic radical R as heteroaryl is a pyridyl, a thienyl, a thiazolyl, a triazolyl, a pyrimidinyl or a thiadiazolyl.
    [9]
    9. Kontaktbijzid according to any one of claims 4 to 8, characterized in that the organic radical R is substituted by hydroxy, mercapto or amino groups.
    [10]
    10. A contact biocide according to any one of claims 7 to 9, characterized in that when using phenyl, alkylphenyl or heteroaryl as the organic radical R this is substituted by a halogen, alkyl, alkoxy, nitro and / or trifluoromethyl group.
    [11]
    11. Kontaktbijzid according to any one of claims 1 to 10, characterized in that the biocidal inactive anion X is a chloride, a bisulfate, a sulfate, a Dihydrogenphosphat-, a hydrogen phosphate, a phosphate, a nitrate, a bicarbonate - is a carbonate or an alkanoate anion. 3 • · •
    12. A method for producing a Kontaktbijzids according to any one of claims 1 to 11, characterized in that first a 2-oxazoline or at least two different 2-oxazolines is cationically ring-opening polymerized or copolymerized and then the recovered polymer is subjected to a partial hydrolysis. Linz, May 3, 2011 KE-KELIT Kunststoffwerk Gesellschaft m.b.H

    Printed: 23-04-2012 E037 102011/00620 Patent Attorneys Dipl.-Ing. Helmut Hübscher Dipl.-Ing. Karl Winfried Hellmich Spittelwiese 7, A 4020 Linz (37877) II A 620/2011, A01N New claims Claims: 1. Use of a compound according to the formula A.

    as a contact biocide, wherein A is a fragment that coordinates as a cation to the lone pair of electrons of a nitrogen atom, B a fragment that reacts as an anion with a carbocation to form an uncharged product, R is an organic radical of a saturated aliphatic chain Ce to C3o saturated cycloaliphatic radical, a monounsaturated or polyunsaturated aliphatic chain having at least 6 carbon atoms, an oligooxazolines crosslinking agent, an aryl spacer to cross-linking oligooxazolines, a phenyl, an alkylphenyl, a heteroaryl or copolymers thereof, and X is a biocidally inactive anion and wherein (n + m)> 10. 2. Use according to claim 1, characterized in that the fragment A is hydrogen, an alkyl Ci to Ce or a benzyl group. 3. Use according to claim 1 or 2, characterized in that the fragment B is a hydroxy group or an amino group. 4. Use according to any one of claims 1 to 3, characterized in that the organic radical R is a saturated aliphatic chain Cg to Cie. 5. Use according to one of claims 1 to 3, characterized in that the organic radical R is a mono- or polyunsaturated aliphatic chain of C8 to C25. 6. Use according to one of claims 1 to 3, characterized in that the cycloaliphatic ring of R is a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyi. 7. Use according to one of claims 1 to 3, characterized in that the organic radical R has a benzyl as alkylphenyl. 8. Use according to one of claims 1 to 3, characterized in that the organic radical R as heteroaryl is a pyridyl, a thienyl, a thiazolyl, a triazolyl, a pyrimidinyl or a thiadiazolyl. 9. Use according to one of claims 4 to 8, characterized in that the organic radical R is substituted by hydroxyl, mercapto or amino groups. 10. Use according to one of claims 7 to 9, characterized in that when using phenyl, alkylphenyl or heteroaryl as organic radical R this is substituted by a halogen, alkyl, alkoxy, nitro and / or trifluoromethyl group. 11. Use according to one of claims 1 to 10, characterized in that the biocidal inactive anion X is a chloride, a bisulfate, a sulfate, a Dihydrogenphosphat-, a hydrogen phosphate, a phosphate, a nitrate, a bicarbonate - is a carbonate or an alkanoate anion. | REPLACED 'Printed: 23-04-2012 IE037 10 2011/00620 3
    [12]
    12. Use according to one of claims 1 to 11, characterized in that first a 2-oxazoline or at least two different 2-oxazolines is polymerized cationically ring-opening or are copolymerized and then the recovered polymer is subjected to a partial hydrolysis. Linz, 20 April 2012 KE-KELIT Kunststoffwerk Gesellschaft m.b.H. by: / Dl Helmut Hübscher / (signed in electronic) FOLLOWING
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    AT6202011A|AT511386B1|2011-05-03|2011-05-03|KONTAKTBIOZID|AT6202011A| AT511386B1|2011-05-03|2011-05-03|KONTAKTBIOZID|
    PCT/AT2012/050059| WO2012149591A1|2011-05-03|2012-05-02|Use of contact biocides based on poly oxazolines|
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