EP2498766A1 - Principes actifs polymères ou oligomères ayant une action biocide, procédé pour les préparer et composition comprenant un principe actif polymère ou oligomère - Google Patents
Principes actifs polymères ou oligomères ayant une action biocide, procédé pour les préparer et composition comprenant un principe actif polymère ou oligomèreInfo
- Publication number
- EP2498766A1 EP2498766A1 EP10805387A EP10805387A EP2498766A1 EP 2498766 A1 EP2498766 A1 EP 2498766A1 EP 10805387 A EP10805387 A EP 10805387A EP 10805387 A EP10805387 A EP 10805387A EP 2498766 A1 EP2498766 A1 EP 2498766A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymeric
- oligomeric
- component
- diamine
- oligomeric active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000004480 active ingredient Substances 0.000 title claims abstract description 62
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 42
- 150000004985 diamines Chemical class 0.000 claims abstract description 35
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 27
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 23
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims abstract description 20
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960004198 guanidine Drugs 0.000 claims abstract description 13
- 229960000789 guanidine hydrochloride Drugs 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical group [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 claims description 66
- 125000001931 aliphatic group Chemical group 0.000 claims description 52
- -1 triethyleneglycol diamine Chemical class 0.000 claims description 28
- 229920002635 polyurethane Polymers 0.000 claims description 26
- 239000004814 polyurethane Substances 0.000 claims description 26
- 239000004416 thermosoftening plastic Substances 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 24
- 239000013543 active substance Substances 0.000 claims description 23
- 229920003023 plastic Polymers 0.000 claims description 22
- 239000004033 plastic Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000155 melt Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000004753 textile Substances 0.000 claims description 15
- 230000000844 anti-bacterial effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 229920000426 Microplastic Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002537 cosmetic Substances 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 239000005022 packaging material Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920002396 Polyurea Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 4
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 3
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims 2
- 230000002349 favourable effect Effects 0.000 abstract description 11
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- 230000002401 inhibitory effect Effects 0.000 description 11
- 239000012634 fragment Substances 0.000 description 8
- 150000002357 guanidines Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000003139 biocide Substances 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000006286 aqueous extract Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000065 atmospheric pressure chemical ionisation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
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- 238000004949 mass spectrometry Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000009717 reactive processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 238000005084 2D-nuclear magnetic resonance Methods 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000013023 gasketing Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- PFRDRCIPKPEULG-UHFFFAOYSA-N imidazol-2-imine Chemical group N=C1N=CC=N1 PFRDRCIPKPEULG-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000001974 tryptic soy broth Substances 0.000 description 1
- 108010050327 trypticase-soy broth Proteins 0.000 description 1
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/785—Polymers containing nitrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
Definitions
- Polymeric or oligomeric active substances with biocidal activity, process for their preparation and composition comprising a polymeric or oligomeric active ingredient
- the invention relates to polymeric or oligomeric active substances with biocidal activity according to the preamble of claim 1, a process for their preparation according to claim 14, a composition comprising a polymeric or oligomeric active substance according to claim 15 and claim 21, a process for the preparation of a composition according to claim 22 and the use of the polymeric or oligomeric active ingredients and the composition according to the invention according to claims 29 and 30.
- Polymers and oligomeric active substances having a biocidal action for example polyguanidines, have been known for a long time. They can be used for a variety of applications.
- US 2,325,586 A describes the preparation of polyguanidines and their salts by means of a polycondensation process. This diamines are reacted with a cyanogen halide, forming a cyanamide. In the subsequent polymerization, the desired polyguanidines or salts thereof are obtained from this cyanamide.
- a special property of such polyguanidines is their biocidal activity.
- EP 0 439 699 A2 provides a solution containing polymers of guanidine salts with increased biocidal activity.
- the object of the invention is therefore to provide novel polymeric or oligomeric active ingredients which have a biocidal effect.
- the invention provides polymeric or oligomeric active agents having biocidal activity obtainable by polycondensation of a guanidine acid addition salt with an amine mixture containing at least one diamine and / or one triamine, wherein at least one amine is selected from the group consisting of i) Diamine having at least one cycloaliphatic radical, and ii) dialkylenetriamine.
- the polymeric or oligomeric active ingredients are the product of a polycondensation of a guanidine acid addition salt with an amine mixture containing at least one diamine and / or a triamine, wherein at least one amine is selected from 4,4'-methylene-bis ( cyclohexylamine) and diethylenetriamine. Both homopolymers and copolymers can be obtained from the amines mentioned.
- guanidine acid addition salt is guanidine hydrochloride.
- a polymeric or oligomeric active ingredient according to the invention is a homopolymer.
- the amine mixture then contains only a single amine compound.
- the polymeric or oligomeric active ingredient may be poly (diethylenetriamine-guanidine hydrochloride) (PDETAG) or polyiminoimidazole. It is advantageous if the amine mixture consists of the triamine diethylenetriamine.
- the homopolymer may also be poly (4,4'-methylenebis (cyclohexylamine) wherein the amine mixture of the diamine is 4,4'-methylenebis (cyclohexylamine).
- a polymeric or oligomeric active ingredient according to the invention is a copolymer, for example a polymeric guanidine derivative.
- the amine mixture then contains at least two different amines. In other words, the amine mixture contains a first component and at least one second component, wherein
- the first component is a diamine or a triamine selected from the group consisting of diamine having at least one cycloaliphatic radical and dialkylenetriamine, wherein
- the second component is a diamine or a triamine selected from the group consisting of diamine having at least one cycloaliphatic radical, dialkylenetriamine, alkylenediamine and oxyalkylenediamine, and
- copolymers result from the combinations of 4,4'-methylenebis (cyclohexylamine) with an amine from the group consisting of diethylenetriamine, hexamethylenediamine, triethyleneglycol diamine and from the combinations of diethylenetriamine with hexamethylenediamine or triethyleneglycol diamine. According to the invention it is therefore advantageous if
- the first component is a diamine or a triamine selected from the group consisting of 4,4'-methylenebis (cyclohexylamine), diethylenetriamine, and wherein
- the second component is also a diamine or a triamine selected from the group 4,4'-methylenebis (cyclohexylamine), diethylene triamine, hexamethylene diamine, triethylene glycol diamine, and
- the first component is 4,4'-methylenebis (cyclohexylamine) and the second component is selected from diethylenetriamine, hexamethylenediamine, triethyleneglycol diamine.
- the first component is diethylene triamine and the second component is selected from hexamethylene diamine and triethylene glycol diamine.
- the mixing ratio of the starting monomers plays an essential role.
- the monomers are present in an equimolar ratio up to a four-fold excess of one of the two monomers. That is, the first component and the second component are present in a molar ratio of 4: 1 to 1: 4, preferably 2: 1 to 1: 2.
- the embodiments of the polymeric or oligomeric active ingredient obtained under these conditions all have an antibacterial activity which can be described by means of the so-called minimum inhibitory concentration. This indicates the lowest bactericidal concentration that inhibits the growth of bacteria in a given solution. In this case, a minimal inhibitory concentration of less than 50 pg / ml is particularly favorable. In many of the embodiments, which are polymeric guanidine derivatives, the minimum inhibitory concentration is even significantly lower and is less than 10 pg / ml or even less than 5 pg / ml. The lower this concentration, the more effectively the corresponding active ingredient can be used as a biocide.
- the polymeric or oligomeric active compounds according to the invention that their minimum inhibitory concentration is 50 pg / ml or less, preferably less than 30 pg / ml, particularly preferably 10 g / ml or less and most preferably less than 5 g / ml.
- a further advantage of the polymeric or oligomeric active compounds according to the invention is the relatively simple production process. It includes the steps
- the process varies slightly, so it is favorable for the preparation of a homopolymer based on 4,4'-methylenebis (cyclohexylamine), for example, when the reaction temperature is 170 ° C.
- a homopolymer prepared on the basis of diethylenetriamine can be recovered at 150.degree.
- the copolymers according to the invention are again preferably produced at 170.degree.
- the invention also provides a composition comprising at least one polymeric or oligomeric active ingredient according to the invention, which is characterized in that the composition is a plastic granulate.
- plastic granules are advantageous in many ways. So it is not only easy to store, but also easy to dose and therefore quickly and easily processable. It can be used, for example, to produce plastic objects, which then have a corresponding biocidal effect by the active substance contained.
- Such articles can play a very advantageous role in many areas of daily life, such as (ex) water pipes, furniture, handles, sanitary ware, shower curtains, sealing material, food packaging, food spouts and spouts, food processing machines, flooring, cleaning wipes, cleaning fluids, agricultural and Feeding equipment, animal blankets, carpets, soles, dental cleaning utensils, drinking vessels, keyboards or other input devices and controls, telephones, antibacterial paints.
- a variety of other items is of course conceivable, for example, clothing textiles, functional textiles, antibacterial papers, technical filters, packaging materials for cosmetics and / or consumer items in the medical field.
- the composition further comprises at least one plastic, preferably at least one thermoplastic polymer, in particular selected from polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polyamide.
- plastic preferably at least one thermoplastic polymer, in particular selected from polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polyamide.
- thermoplastic polymer in particular selected from polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polyamide.
- other polymers which can be selected according to the desired specific use are also conceivable.
- the plastic is a thermoplastic polymer, preferably a thermoplastic polymer selected from the group comprising thermoplastic aliphatic and aliphatic / aromatic polyurethanes, aliphatic and aliphatic / aromatic polyesters, aliphatic and aliphatic / aromatic polyamides, aliphatic and aliphatic / aromatic polycarbonates, aliphatic and aliphatic / aromatic polyureas, aliphatic and aliphatic / aromatic polyester amides, and wherein the polymeric or oligomeric agent has cyclic structures in the main chain.
- a thermoplastic polymer preferably a thermoplastic polymer selected from the group comprising thermoplastic aliphatic and aliphatic / aromatic polyurethanes, aliphatic and aliphatic / aromatic polyesters, aliphatic and aliphatic / aromatic polyamides, aliphatic and aliphatic / aromatic polycarbonates, aliphatic and aliphatic / aromatic polyureas,
- compositions which are present as the hydroxide salt, have a particularly good biocidal activity.
- they may be prepared by basic anion exchange from the corresponding halides, e.g. Chlorides are obtained.
- the polymeric or oligomeric active ingredient has a structure which comprises from the group
- HCl * means here that the HCl is not covalently bound
- n is a natural number, preferably from 1 to 20, more preferably from
- p, q and r are integers representing the preferred molar ratio of
- composition comprising at least one polymeric or oligomeric active ingredient according to one of the claims. 1 to 13, which is obtainable by reaction of
- polymeric or oligomeric drug is covalently bound to the plastic.
- thermoplastic polymer is a thermoplastic aliphatic polyurethane (TAPU) or a thermoplastic aliphatic / aromatic polyurethane (TAAPU) and when the polymeric or oligomeric agent has a cyclic structure selected from the group comprising
- HCl * here also means that the HCl is not covalently bound
- n is a natural number, preferably from 1 to 20, more preferably from 2 to 16 and in particular from 3 to 8, and
- p, q and r are integers representing the preferred molar ratio of
- a copolymer is formed from the components mixed during compounding, if the preparation is carried out under conditions in which a so-called "reactive processing.”
- the polymeric or oligomeric active ingredient is mixed with the thermoplastic polymer and the reaction conditions are selected such that a covalent attachment of the polymeric or oligomeric active ingredient to the thermoplastic polymer takes place, for example, by selecting the thermoplastic polymer such that it still carries reactive groups, such as, for example, isocyanate groups.
- connection can also take place under selected conditions in the context of a recondensation.
- Particularly suitable thermoplastic polymers for this purpose are aliphatic polyurethanes and / or aromatic and / or araliphatic polyurethanes.
- the polymeric or oligomeric active ingredient in liquid form preferably dissolved in a solvent, is reacted with the thermoplastic polymer. It has surprisingly been found that, in particular under these conditions, a covalent bond easily occurs.
- Suitable solvents are, for example, polar solvents such as alcohols, but water is also very suitable.
- thermoplastic polymer at a melt temperature of more than 120 ° C, preferably of more than 140 ° C, more preferably of more than 160 ° C, most preferably from 160 ° C to 300 ° C and very particularly is preferably extruded at 170 ° C and when the thermoplastic polymer with a 0.1 to 90 wt .-% aqueous solution, preferably a 20 to 80 wt .-% aqueous solution, more preferably a 30 to 50 wt .-% aqueous solution, and most preferably a 40 wt .-% aqueous solution of the polymeric or oligomeric active ingredient is added.
- the plastic granules according to the invention can also be provided in the form of a masterbatch. This is then diluted again before use. It is immaterial whether the plastic granulate is a physical mixture of polymeric or oligomeric active ingredient according to the invention or whether the polymeric or oligomeric active ingredient according to the invention is covalently bonded to the thermoplastic polymer.
- plastic granules according to the invention can also be produced in a very rapid and simple way.
- a method of making a plastic granule comprising the steps
- the polymeric or oligomeric active ingredient is preferably added to the thermoplastic polymer in liquid form and the mixing in step a) takes place in an extruder.
- the thermoplastic polymer is selected from the group comprising polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polyamide.
- polymeric guanidine derivatives according to the invention advantageously for the production of clothing textiles, functional textiles, antibacterial papers, technical filters, packaging materials for Food and cosmetics and / or commodities in the medical field can be used.
- gowns, gloves, hoods or shoes that can be used in laboratories or clinical sterile areas, as well as functional textiles such as surgical masks, surgical blankets and bedding using the polymeric or oligomeric active ingredients or a plastic granules of the invention are manufactured.
- cleaning cloths, sterile filters, air filters and the surface of furniture or trays, as well as curtains in the hospital area can be advantageously prepared at least partially using the active compounds of the invention.
- Also advantageous is the use for the production of packaging materials for food or cosmetics.
- the polymeric or oligomeric actives of the invention are for use in the manufacture of (down) water pipes, furniture, handles, sanitary ware, shower curtains, gasketing materials, food packaging, food spouts and spouts, food processing machines, flooring, cleaning wipes, cleaning fluids, agricultural and fodder equipment, animal quilts Carpets, shoe soles, dental cleaning utensils, drinking vessels, keyboards or other input devices and controls, telephone sets, antibacterial paints may be beneficial.
- composition according to the invention for the production of clothing textiles, functional textiles, antibacterial papers, technical filters, packaging materials for food and cosmetics and / or consumer items in the medical field.
- Fig. 2 1 H 1 H COZY spectrum of an aqueous extract of another embodiment of a composition of the invention from a thermoplastic polymer and a polymeric or oligomeric active ingredient according to the invention.
- the flask is equipped with an internal thermometer and a threefold heated reflux condenser with non-return valve according to Stutz (in the following section cooler).
- reaction mixture In an oil bath, the reaction mixture is heated, starting from a temperature of 100 ° C, a slow evolution of gas begins. With further increase in temperature, the gas evolution is only slowly stronger. After a total of 85 minutes, a temperature of 170 ° C is reached.
- the melt is cooled to room temperature.
- the starting amounts used give under the conditions mentioned above 24.48 g of a transparent, colorless and brittle solid.
- the structure of the obtained polymer can be represented by the formula (I).
- N 1 to 8, predominantly 1 to 3.
- radicals R1 and R2 can originate both from the monomer used and from the guanidine hydrochloride used and are therefore defined as follows:
- R1 is selected from H or
- R2 is selected from NH 2 or
- the resulting product mixture thus contains polymeric compounds corresponding to the formulas (II), (III) and (IV):
- formulas (I), (II), (III) and (IV) can also be prepared in an alternative manner, as shown below by way of example for formula (VIII) or (VIII ').
- the positive charge of the guanidine unit is not localized, but is distributed mesomerically to all three nitrogen atoms.
- the melt is maintained at 150 ° C with stirring for five hours until gas evolution ceases.
- the melt Under ice-cooling and oil vacuum, the melt is cooled to room temperature.
- the starting amounts used give 11, 96 g of a white and brittle solid under the conditions mentioned above.
- n 1 to 12, predominantly 2 to 8.
- R3 is either NH 2 or and
- R4 is selected from
- the resulting product mixture thus contains polymeric compounds corresponding to the formulas (VI), (VII) and (VIII):
- HCl * means that the HCl is not covalently bound
- n is a natural number that has the meaning given above
- Example 2 can be represented in an analogous manner, wherein the positive charge mesomerically distributed to all three nitrogen atoms of the guanidine unit.
- the mixing ratio of the two monomers contained in the amine mixture is between 1: 1 and 1: 4 and between 4: 1 and 1: 1.
- the compounds prepared according to one of the preceding examples are prepared in a bacterial nutrient medium, preferably Tryptic Soy Broth, and diluted to various concentrations. These solutions of different concentrations are inoculated with a suspension of Escherichia coli and incubated for 24 h at 37 ° C.
- the minimum inhibitory concentration (MIC) is then understood as meaning the lowest concentration of the biocide to be investigated in the solution in which the growth of the bacteria is inhibited. In the case of the corresponding solution, no cloudiness due to the growth of the bacteria is then observable.
- control polymer As a control, a control polymer was used whose biocidal activity is known and whose minimum inhibitory concentration is usually 5 pg / ml.
- Example 5 Plastic granules with polymeric or oligomeric active ingredient covalently bound to a thermoplastic polymer
- thermoplastic polymers e.g. Polyurethanes come under certain conditions to a so-called Reactive processing.
- the polymeric or oligomeric active ingredients are covalently linked to the thermoplastic used.
- thermoplastic polycondensates namely the polymeric or oligomeric active compounds according to the invention are coextruded with melts of thermoplastic polycondensates or polyaddition products.
- new thermoplastics biocidal thermoplastics
- thermoplastics polycondensates or polyaddition products are used, which are processable by melt extrusion, z.
- polyesters such as polyethylene terephthalate, polybutylene terephthalate, polylactide, polycaprolactone; Polyamides such.
- Polyamide (PA) 6 PA 66, PA 610, PA11, PA12; Polyesteramides, aliphatic and aromatic polycarbonates, aliphatic and aromatic polyurethanes and polyureas.
- water-soluble polyguanidines are used, which are in particular those having the following structures: in which
- HCl * means that the HCl is not covalently bound
- n is a natural number, preferably from 1 to 20, more preferably from
- p, q and r are integers representing the preferred molar ratio of
- thermoplastic melt extrusion in a conventional extruder at extrusion temperatures of 70 - 300 ° C depending on the thermoplastic with an aqueous solution of biocidal or oligomeric active ingredient with concentrations of 0.1 to 90 wt.% Of the biocidal polymer oligomeric drug in water additiviert.
- the water is removed in the evaporation zone of the extruder.
- the new product obtained at the end of the extrusion of the biocidal thermoplastic containing 0.1 to 50% of the structures of the polymeric or oligomeric active ingredients relative to the thermoplastic used.
- the polymeric or oligomeric active ingredients are covalently bound to the thermoplastic by re-condensation. The recondensation takes place during the extrusion.
- thermoplastic polymer used after extrusion can be demonstrated both by NMR and by mass spectrometry.
- thermoplastic aliphatic polyurethane TAPU
- PG1 first polyguanidine
- HCl * means that the HCl is not covalently bound
- n is a natural number that has the meaning given above
- the additivation takes place in such a way that a compound with 10% by weight of the first polyguanidine (PG1) is formed in TAPU.
- the mass spectroscopic analysis shows that after extraction of the compound no active ingredient according to the invention, namely no first polyguanidine (PG1) can be found in the extract.
- the extraction was carried out with boiling water.
- thermoplastic aliphatic / aromatic polyurethane (TAAPU) is used as thermoplastic polymer instead of the thermoplastic aliphatic polyurethane (TAPU).
- TAAPU thermoplastic aliphatic / aromatic polyurethane
- the extrusion was also carried out here at a melt temperature of 170 ° C in a twin-screw extruder with the addition of a 40% aqueous solution of the first polyguanidine (PG1).
- thermoplastic aliphatic polyurethane (TAPU) was extruded as before at a melt temperature of 170 ° C in a twin-screw extruder and additized with a 40% aqueous solution of a second polyguanidine (PG2).
- TAPU thermoplastic aliphatic polyurethane
- PG2 second polyguanidine
- the second polyguanidine (PG2) has the following structure:
- HCl * means that the HCl is not covalently bound
- n is a natural number that has the meaning given above, and p and q are integers that define the preferred molar ratio of the structural fragments to one another in the formulas.
- FIG. 1 shows the 1 H- 1 H COZY spectrum of the extract of the exemplary embodiment.
- Fig. 2 also shows the 1 H- 1 H COZY spectrum of the extract.
- a thermoplastic aliphatic / aromatic polyurethane was used instead of the thermoplastic aliphatic polyurethane (TAPU) and extruded as previously with a 40% aqueous solution of the second polyguanidine (PG2) at a melt temperature of 170 ° C.
- Additization was carried out in such a way that a compound with 10% by weight of the second polyguanidine (PG2) is produced in TAAPU.
- no polymeric or oligomeric drug namely no second polyguanidine (PG2), detectable in the extract with boiling water.
- 1H-1 H-COZY NMR were measured on the Bruker Avance 300 B spectrometer (Dual 1 H - 13C Z-gradient probe), each at 25 ° C in a mixed solvent of hexafluoroisopropanol (ca 1 mL) and D 2 O (ca. 0.2 mL). Calibration was based on the protonated D 2 O peak as an internal standard (4.79 ppm at 25 ° C.). (The 2D spectra shown in the report are not calibrated because the 1 D spectra shift up and left thereby).
- the mass spectra were measured by atmospheric pressure chemical ionization (APCI) on a Thermo Fisher Scientific Finnigan LTQ-FT spectrometer in methanol as a solvent.
- APCI atmospheric pressure chemical ionization
- guanidine acid addition salt with an amine mixture which comprises at least one diamine and / or one triamine, where at least one amine is selected from among A group consisting of i) diamine having at least one cycloaliphatic radical and ii) dialkylenetriamine.
- at least one amine is selected from 4,4'-methylenebis (cyclohexylamine) and diethylenetriamine.
- the guanidine acid addition salt is guanidine hydrochloride.
- an alkylenediamine in particular a compound of the general formula NH 2 (CH 2) n NH 2
- a compound of the general formula NH 2 (CH 2) n NH 2 comprises, or when the amine mixture is a oxyalkylene, particularly a compound is the general Fromel NH 2 [(CH 2) 20] n (CH 2 ) 2 NH 2 , in which n is an integer between 2 and 5, in particular 2, comprises.
- a polymeric or oligomeric active ingredient according to the invention is a homopolymer. It is envisaged that the amine mixture consists of the triamine diethylenetriamine or that the amine mixture consists of the diamine 4,4'-methylenebis (cyclohexylamine).
- the amine mixture contains a first component and at least one second component, wherein
- the first component is a diamine or a triamine selected from the group consisting of diamine having at least one cycloaliphatic radical and dialkylenetriamine, and wherein
- the second component is a diamine or a triamine selected from the group consisting of diamine having at least one cycloaliphatic radical, dialkylenetriamine, alkylenediamine and oxyalkylenediamine, and
- the first component is a diamine or a triamine selected from the group consisting of 4,4'-methylenebis (cyclohexylamine), diethylenetriamine, and wherein
- the second component is a diamine or a triamine selected from the group consisting of 4,4'-methylenebis (cyclohexylamine), diethylenetriamine, hexamethylenediamine, triethyleneglycol diamine and
- polymeric or oligomeric agents in which the first component is 4,4'-methylenebis (cyclohexylamine) and the second component is selected from diethylenetriamine, hexamethylenediamine, triethyleneglycol diamine or the first Component is diethylenetriamine and the second component is selected from hexamethylenediamine and triethyleneglycol diamine, are particularly advantageous. Furthermore, it is favorable if the first component and the second component are present in a molar ratio of 4: 1 to 1: 4, preferably 2: 1 to 1: 2.
- step d) stirring the melt at the temperature set in step d), namely at 140 ° C to 180 ° C, preferably 145 ° C to 175 ° C, more preferably 150 ° C to 170 ° C, until the gas evolution is complete, at least but for 5 hours
- compositions according to the invention comprising at least one polymeric or oligomeric active ingredient according to the invention, wherein the composition is a plastic granulate. It is advantageous if the composition further comprises at least one plastic, preferably at least one thermal polymer, in particular selected from polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polyamide.
- plastic preferably at least one thermal polymer, in particular selected from polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polyamide.
- the plastic is a thermoplastic polymer, preferably a thermoplastic polymer selected from the group comprising thermoplastic aliphatic and aliphatic / aromatic polyurethanes, aliphatic and aliphatic / aromatic polyesters, aliphatic and aliphatic / aromatic polyamides, aliphatic and aliphatic / aromatic polycarbonates, aliphatic and aliphatic / aromatic polyureas, aliphatic and aliphatic / aromatic polyester amides, and wherein the polymeric or oligomeric active agent has cyclic structures in the main chain.
- a thermoplastic polymer preferably a thermoplastic polymer selected from the group comprising thermoplastic aliphatic and aliphatic / aromatic polyurethanes, aliphatic and aliphatic / aromatic polyesters, aliphatic and aliphatic / aromatic polyamides, aliphatic and aliphatic / aromatic polycarbonates, aliphatic and aliphatic / aromatic polyureas,
- the polymeric or oligomeric active ingredient has a structure which comprises from the group
- HCl * means that the HCl is not covalently bound
- n is a natural number, preferably from 1 to 20, more preferably from
- p, q and r are integers representing the preferred molar ratio of
- a process for producing a plastic granulate ie, a process for preparing a composition according to the above, comprising the steps a) combining and mixing a polymeric or oligomeric active substance according to the invention having a biocidal effect with a thermoplastic polymer,
- the polymeric or oligomeric active ingredient is supplied to the thermoplastic polymer in liquid form and the mixing in step a) takes place in an extruder.
- the thermoplastic polymer is selected from the group comprising polyurethane, polyolefin, polyvinyl chloride, polypropylene, polycarbonate, polystyrene, polyethersulfone, silicone and polymaid.
- thermoplastic polymer is a thermoplastic aliphatic polyurethane (TAPU) or a thermoplastic aliphatic / aromatic polyurethane (TAAPU) and when the polymeric or oligomeric active ingredient has a cyclic structure which is selected from the group comprising
- HCl * means that the HCl is not covalently bound
- n is a natural number, preferably from 1 to 20, more preferably from
- p, q and r are integers representing the preferred molar ratio of
- thermoplastic polymer is extruded at a melt temperature of more than 120 ° C, preferably of more than 140 ° C, more preferably of more than 160 ° C and most preferably 170 ° C and if the thermoplastic polymer with a 20 to 50% aqueous solution, preferably a 30 to 50% aqueous solution, more preferably a 40% aqueous solution of the polymeric or oligomeric active ingredient is added.
- composition according to the invention in particular a plastic granules, for the production of clothing textiles, functional textiles, antibacterial papers, technical filters, packaging materials for food and cosmetics and / or consumer items in the medical field.
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Abstract
La présente invention concerne de nouveaux principes actifs polymères ou oligomères ayant une action biocide. De tels principes actifs polymères ou oligomères à action biocide particulièrement avantageux peuvent être obtenus par polycondensation d'un sel d'addition d'acide de guanidine avec un mélange d'amines qui contient au moins une diamine et/ou une triamine, au moins une amine étant choisie dans le groupe qui se compose i) d'une diamine présentant au moins un radical cycloaliphatique, et ii) d'une dialkylène triamine. De préférence, au moins une amine est choisie dans le groupe comprenant 4,4'-méthylène bis(cyclohexylamine) et diéthylène triamine. Il s'avère également utile que le sel d'addition d'acide de guanidine soit de l'hydrochlorure de guanidine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102009052667A DE102009052667A1 (de) | 2009-11-12 | 2009-11-12 | Polymere oder oligomere Wirkstoffe mit biozider Wirkung, Verfahren zu deren Herstellung und Zusammensetzung umfassend einen polymeren oder oligomeren Wirkstoff |
PCT/DE2010/001317 WO2011057611A1 (fr) | 2009-11-12 | 2010-11-12 | Principes actifs polymères ou oligomères ayant une action biocide, procédé pour les préparer et composition comprenant un principe actif polymère ou oligomère |
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EP2498766A1 true EP2498766A1 (fr) | 2012-09-19 |
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EP10805387A Withdrawn EP2498766A1 (fr) | 2009-11-12 | 2010-11-12 | Principes actifs polymères ou oligomères ayant une action biocide, procédé pour les préparer et composition comprenant un principe actif polymère ou oligomère |
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US (1) | US20120259064A1 (fr) |
EP (1) | EP2498766A1 (fr) |
JP (1) | JP2013510909A (fr) |
CN (1) | CN102753160B (fr) |
AU (1) | AU2010317214A1 (fr) |
BR (1) | BR112012011267A2 (fr) |
DE (1) | DE102009052667A1 (fr) |
RU (1) | RU2561606C2 (fr) |
WO (1) | WO2011057611A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102009052721A1 (de) * | 2009-11-12 | 2011-05-26 | B. Braun Melsungen Ag | Verwendung polymerer oder oligomerer Wirkstoffe für medizinische Artikel |
CN103214646A (zh) * | 2013-04-23 | 2013-07-24 | 四川大学 | 具有酶触释药性能的聚氨酯抗菌剂及其制备方法 |
EP3445816B1 (fr) | 2016-04-20 | 2020-01-29 | INEOS Styrolution Group GmbH | Matières à mouler thermoplastiques non pénétrantes à effet antimicrobien |
US11578205B2 (en) * | 2017-01-30 | 2023-02-14 | Lubrizol Advanced Materials, Inc. | Antimicrobial, non-thrombogenic polymer composition |
CA3051427A1 (fr) * | 2017-01-30 | 2018-08-02 | Lubrizol Advanced Materials, Inc. | Polyurethannes thermoplastiques antimicrobiens |
EP3381967A1 (fr) * | 2017-03-28 | 2018-10-03 | Thomas Flechsig | Poly(alkylène)guanidine homogène et son procédé de fabrication |
CA3097111A1 (fr) * | 2018-04-19 | 2019-10-24 | Ucar Health Gmbh | Surface, air, textile, peinture, plastique, silicone et bois, polyethylene; proprietes antimicrobiennes de metal et de derives |
CN109535418B (zh) * | 2018-10-10 | 2019-08-30 | 桂林新先立抗菌材料有限公司 | 一种抗菌织物材料及其制备方法 |
DE102022106745A1 (de) | 2022-03-23 | 2023-09-28 | Werner H. Salewski | Thermoplast-Blends mit inhärent bioziden Eigenschaften |
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US2325586A (en) | 1940-03-21 | 1943-08-03 | Du Pont | Polymeric guanidines and process for preparing the same |
JPS616383A (ja) * | 1984-06-14 | 1986-01-13 | 三洋化成工業株式会社 | 湿潤堅牢度増進剤 |
DE4002404A1 (de) | 1990-01-27 | 1991-08-01 | Degussa | Loesungen polymerer guanidinsalze mit erhoehter biozidwirksamkeit, verfahren zu ihrer herstellung und verwendung |
AT406163B (de) * | 1998-04-22 | 2000-03-27 | P O C Oil Industry Technology | Verfahren zur gewinnung eines desinfektionsmittels |
GB2349644A (en) * | 1999-05-01 | 2000-11-08 | Biointeractions Ltd | Infection resistant polymers, methods for their preparation, and their uses |
KR100557559B1 (ko) * | 1999-12-20 | 2006-03-03 | 에스케이 주식회사 | 폴리헥사메틸렌구아니딘 인산염 분말, 이의 제조방법 및이를 함유한 항균수지 |
UA55660C2 (en) * | 2002-04-05 | 2007-12-25 | Method for treatment of packaging or storage of foodstuffs, mainly, liquid, and packaging treated by this method | |
US20030221330A1 (en) * | 2002-05-31 | 2003-12-04 | Bryan Arnold | Plastic granule dryer system |
ITRM20020529A1 (it) * | 2002-10-18 | 2004-04-19 | Franco Staino | Polimeri sterilizzanti, processo di loro preparazione ed uso. |
RU2239629C1 (ru) * | 2003-07-16 | 2004-11-10 | Общество с ограниченной ответственностью "Международный институт эколого-технологических проблем" | Полибигуаниды линейного и гребенчатого строения |
CN100406496C (zh) * | 2003-07-23 | 2008-07-30 | 上海塑杰科技有限公司 | 一种多元胺与胍盐聚合物及其在抗菌聚酯和聚酰胺材料中的应用 |
RU2264337C1 (ru) * | 2004-07-12 | 2005-11-20 | Общество с ограниченной ответственностью "Международный институт эколого-технологических проблем" | Антимикробный полимерный материал |
AT505102B1 (de) * | 2004-11-05 | 2010-05-15 | Schmidt Oskar | Biozid, insbesondere fungizid wirkendes mittel |
AT502765B1 (de) * | 2005-10-17 | 2008-05-15 | Ke Kelit Kunststoffwerk Gesmbh | Biozide polymere |
WO2009027186A2 (fr) * | 2007-08-29 | 2009-03-05 | Basf Se | Polymères hyperramifiés à unités de guanidine |
CN101173041A (zh) * | 2007-10-19 | 2008-05-07 | 华南理工大学 | 高分子量胍盐和多元胺抗菌型聚合物及其制备方法与应用 |
DE102009052725A1 (de) * | 2009-11-12 | 2011-05-19 | B. Braun Melsungen Ag | Verwendung von Polyoxyalkylendiamin-basierten Polyguanidinderivaten für medizinische Artikel |
DE102009052721A1 (de) * | 2009-11-12 | 2011-05-26 | B. Braun Melsungen Ag | Verwendung polymerer oder oligomerer Wirkstoffe für medizinische Artikel |
-
2009
- 2009-11-12 DE DE102009052667A patent/DE102009052667A1/de not_active Ceased
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2010
- 2010-11-12 WO PCT/DE2010/001317 patent/WO2011057611A1/fr active Application Filing
- 2010-11-12 CN CN201080051466.4A patent/CN102753160B/zh not_active Expired - Fee Related
- 2010-11-12 US US13/509,185 patent/US20120259064A1/en not_active Abandoned
- 2010-11-12 JP JP2012538193A patent/JP2013510909A/ja active Pending
- 2010-11-12 BR BR112012011267A patent/BR112012011267A2/pt not_active IP Right Cessation
- 2010-11-12 EP EP10805387A patent/EP2498766A1/fr not_active Withdrawn
- 2010-11-12 AU AU2010317214A patent/AU2010317214A1/en not_active Abandoned
- 2010-11-12 RU RU2012119073/04A patent/RU2561606C2/ru not_active IP Right Cessation
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Also Published As
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CN102753160A (zh) | 2012-10-24 |
DE102009052667A1 (de) | 2011-05-19 |
RU2561606C2 (ru) | 2015-08-27 |
WO2011057611A1 (fr) | 2011-05-19 |
JP2013510909A (ja) | 2013-03-28 |
CN102753160B (zh) | 2015-12-16 |
AU2010317214A1 (en) | 2012-06-14 |
RU2012119073A (ru) | 2013-12-20 |
US20120259064A1 (en) | 2012-10-11 |
BR112012011267A2 (pt) | 2016-04-12 |
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