• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:

    公开号:AT510155A4
    申请号:T13792010
    申请日:2010-08-17
    公开日:2012-02-15
    发明作者:
    申请人:Sembella Gmbh；
    IPC主号:
    专利说明:

    • · • · • ··
    -1 - {37 496) II
    The invention relates to a composite of a polyaddition on the basis of polyurethane or epoxy resin and at least one polymeric natural substance, which is incorporated via reactive groups in the polymer dressing.
    It is not only known to add plastics, both thermosets and thermosets, with natural fibers such as cellulose, sisal, hemp, wool, silk and the like, to improve the mechanical properties of these plastics, but also these integrate polymeric natural substances into the polymer composite of the composite with the aid of their reactive groups, resulting in material properties for these composites which are decisively determined by the natural substances incorporated in considerable quantities. These reactive groups are in natural products of cellulose and polymeric saccharides by an OH group, in chitin or chitosan by an OH and NH2 group, in silk by a CO-NH group and in wool and hair additionally by an HS group and in natural products of lignins formed by an OH and a COOH group.
    Moreover, it is known to covalently bond natural fibers for microbicidal finishing of cellulosic-based fabrics to a quaternary silane functional-biologically active group by using a silanol coupling coupling group.
    It would be advantageous also to be able to equip polymeric plastics with microbicidal and acaricidal functional groups incorporated into the polymer composite. The invention is therefore based on the object in the polymer composite functional, biolo- • ··· * φ φ φ · · φ • * · φ ·· φ φφ φ φ φφ «'Φφ I * Φ φ' φ φφ φφ« · φ φφ φφ φφ φ φφ φφφφ -2- gisch effective groups in particular for microbicidal and acaricidal equipment of the plastic incorporate.
    Starting from a composite material of the type described above, the invention solves the stated object in that the polymeric natural substances are covalently bound via coupling spacers to functional groups, in particular for the microbicidal and / or acaricidal finishing of the polyaddition polymer.
    The invention is based on the finding that, although functional groups for a microbicidal and acaricidal equipment can not be incorporated directly into the polymer structure via polymeric natural substances, polyaddition polymers based on polyurethane or epoxy resin can be used as plastics. The microbicidal and acaricidally active functional groups can be covalently bound to the polymeric natural substances via coupling spacers before these natural-group-containing natural substances are incorporated in a manner known per se into the matrix of the polyadditered polymers via their reactive groups.
    When using polyurethane-based plastics, the reactive groups such as OH, NH 2, COOH, CONH and HS, the fibers in the course of the usual reaction of isocyanate and polyol are reacted with the isocyanate group of the polyurethane formulation, resulting in a particularly strong composite between the functionalized polymeric natural products and the polyurethane.
    Similarly, polymeric natural products to which functional groups are attached as active agents via coupling spacers can be incorporated into the polyaddition polymer matrix. Instead of the isocyanate group, the reactive oxirane group merely undergoes a polyaddition reaction with the reactive groups of the polymeric natural products. T t · · · · · · t t · t · t · t · t · t
    Irrespective of whether the polymeric natural products containing the biologically active functional groups are incorporated into the matrix of a polyurethane or of an epoxy resin, it has surprisingly been found that these functional groups are active in the entire composite despite a comparatively small proportion of the natural substances provide effective microbicidal or acaricidal equipment of composites.
    Particularly suitable as polymeric natural substances are cellulose, hemicellulose, starch, dextrin, cyclodextrin, chitin, chitosan, lignin, wool and silk, because these polymeric natural substances are advantageously incorporated on the one hand via their reactive groups into the structure of the polyaddition polymers and, on the other hand, are covalently bound biologically via appropriate coupling spacers effective, functional groups can be bound. Suitable functional groups for a microbicidal equipment of a composite according to the invention are, in particular, a biguanide, polybiguanide, polyamine, polyaminoacrylate, sulfonamide or a silver-copper-zinc complex.
    With pyrithione, permethrin, tea tree oil, abamectin, neonicotinoid, fibronil or spi-romesifen as functional group bound to the polymeric natural product polyaddition polymers can be acaricidal equipped.
    As a coupling spacer between the respective polymeric natural substance and the biologically active, functional groups, different substances with corresponding reactive groups can be provided. For example, it is possible to use silanes or siloxanes with reactive groups, such as halogen, alkoxy, epoxide or amine, as coupling spacers. However, suitable coupling partners are also 1,2,5-triazines having reactive groups, such as halogen, alkoxy, amine or hydroxy. Another possibility for Kupplspacer results from the use of bis (2-oxazolines), such as 1,3-phenylene-bis (2-oxazoline) or 1,1-carbonyl-bis (capro-lactam). These substances are commonly used as so-called chain extenders for polyamides or polyesters. • · · * * 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 · 999 In the event that the polymeric natural product and / or the biologically active functional group has a thiol or carboxyl group, an at least doubly charged cation, in particular zinc, copper, iron, beryllium or germanium, is recommended as a coupling spacer
    In the following, non-limiting examples, the invention is explained in more detail.
    Example 1:
    A solution of 40 g of y-cyclodextrin in 60 g of water at 50 ° C with stirring with 12.6 g of sulfadiazine-Na (0.05 mol), forming a water-soluble complex. By adding 0.85 g of silver nitrate in 15 ml of water, the silver salt of the sulfadiazine / cyclodextrin complex is precipitated. After filtering, washing and drying, 50.7 g of Intermediate 1 is obtained.
    Example 2:
    A suspension of 50 g of wool powder in 250 ml of water is stirred with 2 g of NaOH at 40 ° C over a period of 30 minutes to form the Na salt of the thiol group derived from cysteine molecules in the peptide chain of the wool. By addition of 1.36 g of zinc chloride (0.01 mol) and immediately thereafter of 3 g of a 50% Pyrithionnatrium solution an active complex of the structure wool-zinc pyrithione is obtained. After filtration, washing and drying, 51.5 g of an intermediate 2 are obtained as a white powder.
    Example 3: 100 g of cellulose powder obtained by grinding from beech cellulose fibers obtained by the Lycocell method are homogenized in 500 ml of water to give a viscous suspension. To this suspension are added 10 g of a 50% by volume aqueous solution of an addition product of 3-chloropropyltrimethoxy-silane with dimethyldodecylamine at 40 ° C. *** "" * II "" C. and the mixture stirred for one hour. The hydrolyzed methoxyl groups in the silane react with the hydroxyl groups of the cellulose to form a stable, water-insoluble active complex of the structure cellulose-silane-quaternary amine. Filtration, washing and drying yield 103 g of intermediate 3 in the form of light, fluffy flakes.
    Example 4: 50 g of a commercially available 50% strength aqueous solution of polyhexamethylene biguanide hydrochloride are freed in suspension with 500 ml of toluene in a Dean-Stark apparatus by distillation from the aqueous fraction, whereby an anhydrous suspension of Polyhexamethylenbiguanidchlorwasserstoff formed in toluene. 120 g of chitosan powder and 2.25 g (0.1 mol) of phenylene-1,3-bis (oxacoline) are introduced into this suspension and allowed to react for two hours under reflux. The usual isolation by filtration, washing and drying results in 135.6 g of an intermediate 4 in the form of a brown-yellow powder having the structure chitosan-phenylene-1,3-dicarbonamido-polyhexamethylene biguanide.
    Example 5:
    As Example 4, but instead of phenylene-bis (oxacoline) 2.55 g of 1,1-carbonyl-bis (caprolactam) are used. The resulting intermediate 5 has the structure chitosan-hexamethylcarbonamido-polyhexamethylene biguanide.
    Example 6: 1.87 g (0.01 mol) of 2,6-dichloro-4-hydroxy-1,3,5-triacin / Na salt in 100 ml of water (obtained from trichlorotriazine and NaOH in water at temperatures below 5) ° C) are mixed with an aqueous solution of 1.4 g Polyhexamethylenbiguanidchlorwasserstoff in 2 g of water and with 0.8 g (0.02 mol) of NaOH in 10 ml of water at Φ 9 9 9 9 9 9 9 9 9 Mit 9 9 99 9 99 ············································································································································································································· touched. Here, another chlorine atom of the triazine structure connects to the biguanide group. After the reaction time, a suspension of 50 g of silk powder in 250 ml of water is added to the solution and heated to 80 ° C before 2 ml of 40% hydrochloric acid are added. The result is an active complex of the structure silk - triazinyl polyhexamethylene biguanide. After filtration, washing and drying, 51.2 g of an intermediate 6 in the form of a yellowish powder are obtained.
    Analogously to Examples 1 to 6, active complexes were prepared as intermediates, as indicated below.
    Intermediate 7: Cellulose triazinyl polyimine Intermediate 8: Lignin triazinyl polyhexamethylene biguanide Intermediate 9: Chitosan triazinyl pyrithione Intermediate 10: Cellulose silane pyrithione Intermediate 11 Chitosan silane pyrithione Intermediate 12 Chitosan triazinyl polyhexamethylene biguanide Intermediate 13 Wool-triazinyl-polyhexamethylene biguanide Intermediate 14: wool-silane-quaternary amine Intermediate 15: chitosan-silane-quaternary amine
    To produce a flexible polyurethane foam in the usual composition of polyol, isocyanate, water, stabilizers and catalysts, the components are added to the components in the total amount 1 to 10 wt.% Of the intermediates 1 to 15 before the foaming is initiated in a known manner. The individual samples were numbered according to the numbers of intermediates used, so that sample 1 contains intermediate 1 and sample 15 contains intermediate 15. The individual samples were subjected to various microbiocidal and acaricidal experiments.
    Ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ftp · · »Ft -7-
    The microbial assay was performed according to JIS Z 2801: 2000 with Eschericia coli DSM 787 and Staphylococcus aneus DSM 346. The value R of the antimicrobial activity was determined for Gram-positive and Gram-negative bacteria.
    Fungal growth was tested according to ISO 846, both by Method A, which is suitable for evaluating the resistance of the sample to fungal infestation, if no other usable organic materials are present, and by Method B, which detects the situation of surface contamination of the fungi Sample in practice reflects.
    The acaricidal activity was tested in the long-term test by means of the heat escape method {SOP No. 9-009), whereby a sample of 10 × 10 cm was soiled with 1 g of artificial house dust, provided with mite feed consisting of whiskers and yeast extract, and placed in a petri dish. The artificial house dust was previously mixed with house dust mites. The biotopes were incubated for four weeks in a humid chamber at 70 to 80% relative humidity and at a temperature between 20 and 25 ° C. At the end of the incubation period, the biotopes were covered with adhesive film, placed on a hot plate and covered with an opaque plate. The starting temperature of 25 ° C was continuously increased until it reached 40 ° C in the biotopes. After one hour, the films were peeled off and glued onto plastic wrap. The process was repeated at a temperature of 45 ° C. The bottom thermal effect causes a reduction in relative humidity and causes the mites to travel upward into cooler and moist air layers. They are fixed to the adhesive film. The mites on the film were counted by means of a grid under a stereomicroscope, with the indicated number of mites recovered being related to 100 exposed mites.
    The test results are summarized in the table below and compared with an untreated sample 16. In column 1, the number of the respective sample, in column 2, the proportion by weight of the respective intermediate product ZwP in wt.%, In column 3, the density of the polyurethane foam in • · · · · * «φ φ φ · t φ I φ φφ φ Φ · · φ φ φ · # φ »· φ · I φ f φ φ φφ · ·« φφ φφ φ · φφφφ -8 kg / m3, in columns 4 and 5 the value R of the antimicrobial activity for gram-positive (grampos.) and gram-negative (gramneg.) bacteria, in column 6 the A and B values for fungal infestation (fungus) and in column 7 the number of mites recovered (milz).
    Sample No. ZwP Density R-value Mushroom Mil. gram pos. Gram-negative. 1 1.5 39.8 3.0 3.0 A00 B01 10 2 3.0 40.1 4.0 4.0 A00 B00 0 3 6.5 40.4 2.7 4.4 A00 B01 50 4 5 , 0 40.1 3.7 4.0 A01 B01 40 5 5.0 40.1 3.8 3.9 A00 B01 30 6 3.0 40.0 4.0 4.1 A00 B00 0 7 6.5 40.5 2.2 2.7 A01 B11 10 8 8.5 42.1 4.1 4.2 A01 B01 30 9 4.0 39.8 3.7 4.1 A00 B00 0 10 5.5 40, 0 2.8 4.8 A00 B00 0 11 5.0 39.9 3.2 4.3 A00 B00 0 12 4.0 39.7 4.1 4.0 A00 B01 10 13 5.0 39.9 4 , 4 4.5 A00 B00 0 14 4.5 39.9 3.8 4.0 A00 B00 0 15 4.5 40.0 3.9 4.1 A00 B01 10 16 39.8 1 1 A23 B34 100
    In addition, further samples were examined according to the following examples. 378 g of bisphenol A di-glycidyl ether (1 mol) are finely ground with 250 g of talcum, 45 g of micaceous mica, 120 g of T1O2, 1.2 g of bentonite and 60 g of the intermediate product 3. ······ Mixture of butyl acetate and methyl isobutyl ketone (1: 1) diluted to a spreadable paint. (Solids content 60%). 150 g of this varnish are mixed with 15 g of triethylenetetramine in 15 ml of butyl acetate as hardener, mixed well and the varnish is spread over 1 hour on concrete as a wear layer. Drying within 3 hours, complete hardening after 2 days.
    A test sample is subjected to the microbicidal test according to JIS Z 2801 and the fungus growth test according to ISO 846 and shows that the coating does not allow fungal growth or colonization with bacteria. This coating is therefore well suited as a covering for sterile rooms.
    Furthermore, a polyurethane foam formulation in a known composition (polyol OH number 450, MDI isocyanate, stabilizers, catalysts and Cyc lopentan as blowing agent) with 10 wt.% (Based on total formulation, except cyclopentane) of the intermediates 2, 7, 9, 10 and 11 and foamed to an insulating foam with a density of 55-60 kg / m3.
    Samples of these rigid polyurethane foams were tested for fungal growth according to ISO 846. In no case was fungal growth observed on the insulator, i. H. The polyurethane rigid foam formulations of this type are suitable for insulating panels used in wetlands with a particularly pronounced tendency to fungal attack.
    权利要求:
    Claims (6)
    [1]
    I # «« II t "It ········································································································································································································ «· Patent Attorneys Dipl.-Ing. Helmut Hübscher Dipl.-Ing. Karl Winfried Hellmich Spittelwiese 7, A 4020 Linz (37496) II Claims 1. Composite of a polyaddition polymer based on polyurethane or epoxy resin and at least one polymeric natural substance, which is incorporated into the polymer dressing via reactive groups, characterized in that the polymeric natural substances are covalently bonded to functional groups, in particular to the microbicidal and / or acaricidal equipment of the polyaddition polymer, via coupling spacers.
    [2]
    2. Composite according to claim 1, characterized in that as a polymeric natural substance at least one substance from the cellulose, hemicellulose, starch, dextrin, cyclodextrin, chitin, chitosan, lignin, wool and silk contained group is used.
    [3]
    3. A composite according to claim 1 or 2, characterized in that for a microbicidal equipment a biguanide, polybiguanide, polyamine, polyaminoacrylate, sulfonamide or a silver-copper-zinc complex is bonded as a functional group to the polymeric natural product.
    [4]
    4. Composite according to claim 1 or 2, characterized in that for an acaricidal equipment pyrithione, permethrin, tea tree oil, abamectin, neonicotinoid, fibronil or spiromesifen is bound as a functional group to the polymeric natural product.
    [5]
    5. A composite according to any one of claims 1 to 4, characterized in that as a coupling spacer between the polymeric natural product and the functional groups, a silane or siloxane having reactive groups, such as halogen, alkoxy, epoxy or amine, 1,2,5-triazine with reactive groups such as halogen, alkoxy, amine or hydroxy, or bis (2-oxazoline), such as 1,3-phenylene-bis (2-oxazoline) or 1,1-carbonyl-bis (caprolactam) is used.
    [6]
    6. Composite according to one of claims 1 to 4, characterized in that when using a polymeric natural product and / or a functional group having a thio or carboxyl group as a coupling spacer used at least twice-charged cations, in particular zinc, copper, iron, beryllium or germanium is. Linz, on 16 August 2010 Sembella GmbH by

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    引用文献:
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    法律状态:
    2013-08-15| PC| Change of the owner|Owner name: KARL RAMETSTEINER, AT Effective date: 20130625 |
    2013-11-15| PC| Change of the owner|Owner name: BRECKLE CHEMICALS&TECHNICS GMBH, DE Effective date: 20131010 |
    2019-04-15| MM01| Lapse because of not paying annual fees|Effective date: 20180817 |
    优先权:
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    AT13792010A|AT510155B1|2010-08-17|2010-08-17|COMPOSITE OF A POLYADDITION POLYMER|AT13792010A| AT510155B1|2010-08-17|2010-08-17|COMPOSITE OF A POLYADDITION POLYMER|
    EP20110450103| EP2420521B1|2010-08-17|2011-08-12|Composite of a polyaddition polymer|
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