WO2023027438A1 - 탄성 항균 폴리우레탄, 그 제조방법 및 이를 포함하는 물품 - Google Patents
탄성 항균 폴리우레탄, 그 제조방법 및 이를 포함하는 물품 Download PDFInfo
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- WO2023027438A1 WO2023027438A1 PCT/KR2022/012465 KR2022012465W WO2023027438A1 WO 2023027438 A1 WO2023027438 A1 WO 2023027438A1 KR 2022012465 W KR2022012465 W KR 2022012465W WO 2023027438 A1 WO2023027438 A1 WO 2023027438A1
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- WIPO (PCT)
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- polyurethane polymer
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- antibacterial polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 99
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 98
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 92
- 125000004432 carbon atom Chemical group C* 0.000 claims description 102
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- -1 isocyanate compound Chemical class 0.000 claims description 56
- 150000003077 polyols Chemical class 0.000 claims description 43
- 229920005862 polyol Polymers 0.000 claims description 37
- 150000002009 diols Chemical class 0.000 claims description 32
- 125000002947 alkylene group Chemical group 0.000 claims description 31
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012948 isocyanate Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 23
- 229920000570 polyether Polymers 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 125000000732 arylene group Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 12
- 125000002723 alicyclic group Chemical group 0.000 claims description 11
- 125000005549 heteroarylene group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 9
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 238000009864 tensile test Methods 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 17
- 239000000178 monomer Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000009987 spinning Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 230000000845 anti-microbial effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229920002334 Spandex Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000004759 spandex Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 210000002390 cell membrane structure Anatomy 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005332 alkyl sulfoxy group Chemical group 0.000 description 1
- 125000005377 alkyl thioxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000003974 aralkylamines Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 125000005165 aryl thioxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
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- 125000005462 imide group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3806—Polyhydroxy compounds having chlorine and/or bromine atoms
- C08G18/381—Polyhydroxy compounds having chlorine and/or bromine atoms having bromine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- This application relates to elastic antibacterial polyurethane and a manufacturing method thereof.
- the present application relates to an article comprising the elastic antibacterial polyurethane.
- Polyurethane one of engineering plastics, is used in various fields such as synthetic fibers, paints, and interior materials for vehicles.
- polyurethane can be used with nylon to make up a synthetic fiber called spandex, which can be used for underwear, socks, swimwear, and the like.
- spandex a synthetic fiber called spandex
- polyurethane since polyurethane has a three-dimensional foam structure, it is elastic and robust, and thus is widely used in mattresses and fabrics, as well as foam sponges.
- One object of the present application is to provide a polyurethane having excellent elasticity and antibacterial properties.
- Another object of the present application is to provide a polyurethane having excellent heat resistance.
- Another object of the present application relates to an article comprising a polyurethane of the above characteristics.
- the present application relates to elastic antibacterial polyurethane polymers and methods of making the same.
- the polyurethane polymer of the present application has excellent antibacterial properties, heat resistance (durability) and tensile properties and the like.
- alkyl group may be an alkyl group having 1 to 40 carbon atoms.
- the alkyl group has 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 8 carbon atoms.
- It may be an alkyl group of 4.
- the alkyl group may be a straight-chain, branched-chain or cyclic alkyl group.
- the alkyl group may be optionally substituted with one or more substituents.
- haloalkyl group may refer to a compound in which a hydrogen atom of an alkyl group is substituted with a halogen atom.
- the alkyl group may be used in the same meaning as described above.
- alkenyl group may be an alkenyl group having 2 to 40 carbon atoms.
- the alkenyl group has 2 to 36 carbon atoms, 2 to 32 carbon atoms, 2 to 28 carbon atoms, 2 to 24 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 carbon atoms. to 4 alkenyl groups.
- the alkenyl group may be a linear, branched or cyclic alkenyl group.
- the alkenyl group may be optionally substituted with one or more substituents.
- alkynyl group may be an alkynyl group having 2 to 40 carbon atoms.
- the alkynyl group has 2 to 36 carbon atoms, 2 to 32 carbon atoms, 2 to 28 carbon atoms, 2 to 24 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 carbon atoms. to 4 alkynyl.
- the alkynyl group may be a straight-chain, branched-chain or cyclic alkynyl group.
- the alkynyl group may be optionally substituted with one or more substituents.
- aryl group refers to a benzene ring structure, or two or more benzene rings connected while sharing one or two carbon atoms, or linked by an arbitrary linker. It may mean a monovalent residue derived from a compound or a derivative thereof containing a structure having
- the aryl group may be an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. In this case, the aryl group may be optionally substituted with one or more substituents.
- heteroaryl group may mean an aryl group containing one or more of O, N, Si, and S.
- the aryl group may be used in the same meaning as described above.
- the hetero aryl group may have 2 to 30 carbon atoms.
- aryloxy group may mean a group RO- in which R is an aryl group.
- the allyl group may be used in the same meaning as described above.
- an "alkoxy group” may be an alkoxy group having 1 to 40 carbon atoms.
- the alkoxy group has 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 8 carbon atoms.
- 4 may be an alkoxy group.
- the alkoxy group may be a straight-chain, branched-chain or cyclic alkoxy group.
- the alkoxy group may be optionally substituted with one or more substituents.
- alicyclic structure is a cyclic hydrocarbon structure other than an aromatic ring structure, and may mean a compound represented by -Y.
- the alicyclic ring structure may be, for example, an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms.
- the alicyclic structure may be optionally substituted with one or more substituents.
- heteroalicyclic structure may mean an alicyclic structure including one or more of O, N, Si, and S.
- an alicyclic structure may be used in the same meaning as described above.
- alkylthio group may mean RS-, where R is an alkyl group.
- R is an alkyl group.
- the alkyl group may be used in the same meaning as described above.
- arylthio group may mean RS-, where R is an aryl group.
- the aryl group may be used in the same meaning as described above.
- direct bond means a case where no atom exists at a position that can be a direct bond.
- an "alkylene group” may be an alkylene group having 1 to 40 carbon atoms.
- the alkylene group has 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 carbon atom. to 4 alkylene groups.
- the alkylene group may be a straight-chain, branched-chain or cyclic alkylene group.
- the alkylene group may be optionally substituted with one or more substituents.
- a "heteroalkylene group” may be an alkylene group containing one or more of O, N, Si, and S.
- the alkylene group may be used in the same meaning as described above.
- a "cycloalkylene group” is a divalent functional group derived from a cycloalkane and may have 3 to 20 carbon atoms.
- the cycloalkylene group may be a cycloalkylene group having 3 to 15 carbon atoms, 3 to 10 carbon atoms, or 3 to 5 carbon atoms.
- the cycloalkylene group may be optionally substituted with one or more substituents.
- an "arylene group” may mean a divalent aromatic hydrocarbon group.
- the arylene group includes a benzene ring structure, or a structure in which two or more benzene rings are connected while sharing one or two carbon atoms, or are connected by an arbitrary linker, or a compound or derivative thereof It may mean a divalent residue derived from.
- the arylene group may be an arylene group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. In this case, the arylene group may be optionally substituted with one or more substituents.
- heteroarylene group may be an arylene group containing one or more of O, N, Si, and S.
- the arylene group may be used in the same meaning as described above.
- the hetero arylene group may have 2 to 30 carbon atoms.
- the above-mentioned groups may be substituted or unsubstituted.
- substituted or unsubstituted refers to deuterium; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of hetero
- a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
- the number of carbon atoms in the aforementioned group may mean the number of carbon atoms in the length of the main chain or the number of carbon atoms in the main backbone.
- the elastic antibacterial polyurethane polymer includes a predetermined unit means that a unit derived therefrom is included in the polymer structure as the compound is polymerized in a polymer structure (main chain or side chain) formed by the reaction of one or more compounds. can do.
- molecular weight may be a weight average molecular weight (eg, g/mol) in terms of polystyrene measured by GPC.
- the present application is directed to a resilient antimicrobial polyurethane.
- Polyurethane described below has excellent antibacterial properties, mechanical properties (eg, tensile strength, tensile strain) and heat resistance.
- the elastic antibacterial polyurethane of the present application includes (A) an isocyanate compound; and (B) a unit derived from a polyol comprising polyether glycol and a diol represented by Formula 1 below, wherein the polyol (B) includes 0.01 to 40 mol% of the diol represented by Formula 1.
- R1 and R2 are each independently hydrogen, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, or an alkylthio group or an aryl group. is tigi,
- L1 and L2 each independently, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group;
- L3 is a direct bond, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group;
- A is an alkylene group having more than 6 carbon atoms
- X - means an anion
- the number of carbon atoms of A in Formula 1 may mean the number of carbon atoms in the main chain.
- the elastic antimicrobial polyurethane of the present application is prepared by reacting an isocyanate compound with a polyol component including at least two different polyols, that is, polyether glycol and a compound of Formula 1 (quaternary ammonium diol) may have been
- the type of the (A) isocyanate compound is not particularly limited, and, for example, the isocyanate compound may be selected in consideration of physical properties (eg, processability, heat resistance, etc.) of the polymer and reactivity between polymer forming components.
- the isocyanate compound used to form the polyurethane may be an aromatic isocyanate.
- aromatic isocyanate can compensate for the low heat resistance of the ammonium diol represented by Chemical Formula 1.
- an isocyanate compound included in polyurethane toluene diisocyanate, xylene diisocyanate, methylene diphenyl diisocyanate (MDI), or any of the compounds listed above
- An aromatic isocyanate compound having a skeleton or the like can be used.
- the aromatic isocyanates used in preparing the polymers of the present application are not limited to those listed above.
- the (B) polyol may mean an alcohol compound including two or more hydroxyl groups.
- the polyol includes (b1) polyether glycol and (b2) a diol represented by Formula 1.
- the polyether glycol (b1) is a major component enabling the elastic properties of the polyurethane of the present application to be secured.
- polyether glycol used is not particularly limited.
- poly(tetramethylene ether) glycol (PTMG) or polypropylene glycol (PPG) may be used.
- the polyether glycol may have a weight average molecular weight in the range of 500 to 3000.
- the lower limit of the molecular weight is 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, 1100 or more, 1200 or more, 1300 or more, 1400 or more, 1500 or more, 1600 or more, 1700 or more, 1800 or more, 1900 or more, 2000 or more, 2100 or more, 2200 or more, 2300 or more, 2400 or more, or 2500 or more
- the upper limit is, for example, 2900 or less, 2800 or less, 2700 or less, 2600 or less, 2500 or less, 2400 or less, 2300 or less, 2200 or less.
- the polyether glycol may have a weight average molecular weight of 1000 or more or 1500 or more, and 2500 or less or 2000 or less.
- molecular weight of polyether glycol is appropriately adjusted within the above range, it is advantageous to secure mechanical properties (eg, elasticity or tensile properties).
- the diol component (b2) represented by Formula 1 may impart antibacterial properties to polyurethane.
- R1 in Formula 1 is, except for hydrogen, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure Or it may be an alkylthio group or an arylthio group.
- Polyurethanes containing units derived from quaternary ammonium monomers in the form of diols (or diol-based quaternary ammonium monomers) are more advantageous in providing excellent antibacterial properties.
- the A may be an alkylene group having more than 6 and 20 carbon atoms, more specifically, 8 to 20, 8 to 18, 8 to 16, 8 to 14, 8 to 12, or 8 to 10 carbon atoms.
- a of Formula 1 is an alkylene group satisfying the above number of carbon atoms, it is advantageous in imparting excellent antibacterial properties and low toxicity to the compound of Formula 1 or the polyurethane polymer.
- A may be a straight-chain alkylene group.
- the ammonium cation is adsorbed on the anionic membrane of bacteria, and the straight-chain alkylene group, that is, the hydrophobic group A of Formula 1 destroys the cell membrane structure of the bacteria to release proteins and enzymes, and has an antibacterial effect.
- the antibacterial action by destroying the cell membrane structure may be more effective when A has a structure favorable to cell membrane penetration of bacteria while securing some degree of hydrophobicity.
- the A may have a structure represented by Formula 2 below.
- n is a number of 4 or more (for example, n is 4 or more, 5 or more, or 6 or more), and L3 and R2 may be respectively bonded to both ends indicated by *. However, when L3 is a direct bond, one end indicated by * is bonded to the N atom.
- n in Formula 2 becomes too large, the toxicity of the compound or polymer of Formula 1 may increase.
- the upper limit of n may be, for example, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less.
- R1 and/or R2 in Formula 1 may be a straight-chain alkyl group.
- R1 and/or R2 of Formula 1 may be an alkyl group having 12 or less, 8 or less, or 4 or less carbon atoms. Specifically, R1 and/or R2 may be a propyl group, an ethyl group or a methyl group.
- R1 and R2 in Formula 1 may be the same as each other.
- L1 and/or L2 may be a straight-chain alkylene group.
- L1 and/or L2 in Formula 1 may be an alkylene group having 12 or less, 8 or less, or 4 or less carbon atoms.
- L1 and/or L2 may be a propylene group, an ethylene group, or a methylene group.
- L1 and L2 may be identical to each other.
- the L3 may be a straight-chain alkylene group.
- L3 may be an alkylene group having 12 or less carbon atoms, 8 or less carbon atoms, or 4 or less carbon atoms.
- L3 may be a propylene group, an ethylene group, or a methylene group.
- X - is F - , Cl - , Br - , I - , NO 3 - , (CN) 2 N - , BF 4 - , ClO 4 - , RSO 3 - (Where R is 1-C 9 alkyl group or phenyl group), RCOO - (where R is an alkyl group or phenyl group having 1 to 9 carbon atoms), PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , (CF 3 SO 3 - ) 2 , (CF 2 CF 2 SO 3 - ) 2 , (C 2 F 5 SO 2 ) 2 N - , (CF 3 SO 3 ) 2 N - , (CF 3 SO 2 )
- the molecular weight of the monomer represented by Formula 1 may be adjusted in consideration of antibacterial properties. For example, if the molecular weight is large for reasons such as too many carbon atoms of other groups bonded to N atoms constituting ammonium of Formula 1, toxicity harmful to the human body may be expressed. In addition, it is difficult to secure sufficient antibacterial activity when the molecular weight is low for the same reason as the number of carbon atoms of other groups bonded to the N atom constituting ammonium is too small.
- the compound represented by Chemical Formula 1, that is, the ammonium monomer in the form of a diol may have a weight average molecular weight of 300 or more.
- the lower limit of the weight average molecular weight of the diol-type ammonium monomer may be 310 or more, 320 or more, 330 or more, 340 or more, 350 or more, 360 or more, 370 or more, 380 or more, 390 or more, or 400 or more.
- the upper limit may be 500 or less.
- the upper limit of the weight average molecular weight of the diol-type ammonium monomer is, for example, 490 or less, 480 or less, 470 or less, 460 or less, 450 or less, 440 or less, 430 or less, 420 or less, 410 or less, 400 or less, 390 It may be 380 or less, 370 or less, 360 or less, or 350 or less.
- the polyol (B) includes 0.01 to 40 mol% of the diol represented by Formula 1.
- the content of the diol represented by Formula 1 in the polyol (B) is, for example, 0.05 mol% or more, 0.1 mol% or more, or 0.5 mol% or more, specifically 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, 15 mol% or more, 16 mol% or more, 17 mol% or more, 18 mol% or more, 19 mol% or more, 20 mol% or more, 21 mol% or more, 22 mol% or more, 23 mol% or more, 24 mol% or more, 25 mol% or more, 26 mol% or more, 27 mol% or more, 28 mol% or more, 29 mol% or more, 20
- the upper limit is, for example, 39 mol% or less, 38 mol% or less, 37 mol% or less, 36 mol% or less, 35 mol% or less, 34 mol% or less, 33 mol% or less, 32 mol% or less, 31 mol% or less, 30 mol% or less, 29 mol% or less, 28 mol% or less, 27 mol% or less, 26 mol% or less, 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, 11 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, or 5 mol% or less
- the content of polyether glycol in the polyol (B) may be, for example, the remaining amount after excluding the content (mol %) of the diol represented by Chemical Formula 1 in the polyol.
- the content of polyether glycol in the polyol (B) is 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more or 95 mol% or more.
- the upper limit is, for example, 99.99 mol% or less, 99.95 mol% or less, 99.9 mol% or less, or 99.5 mol% or less, specifically 99 mol% or less, 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, or 65 mol% or less.
- the molar ratio of (A) isocyanate to the polyol (B) may be in the range of 1.0 to 2.0. At this time, the molar ratio means dividing the number of moles of the isocyanate compound used in polymer production by the total number of moles of the polyol.
- the lower limit of the molar ratio of (A) isocyanate to polyol (B) may be 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, or 1.9 or more.
- the upper limit may be, for example, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, or 1.2 or less.
- the polyurethane polymer is an isocyanate compound, methylenediphenyl diisocyanate (MDI); polytetramethylene glycol (PTMG), which is a polyether glycol; and a unit derived from the compound of Formula 1.
- MDI methylenediphenyl diisocyanate
- PTMG polytetramethylene glycol
- the polyurethane polymer may include a structure represented by the formula below.
- n may be an integer capable of satisfying the above-described molecular weight of polyether glycol.
- m in the above structural formula may be an integer that satisfies the molecular weight of the urethane polymer to be described later, for example, it may be 3 to 100.
- the polyurethane polymer may further include a unit including methylenediphenyl diisocyanate (MDI), which is an isocyanate compound, and polytetramethylene glycol (PTMG), which is a polyether glycol, in addition to the unit represented by Structural Formula 1. (ie, a unit that does not include a unit derived from the compound of Formula 1). Such a unit does not include a unit derived from Formula 1 in Structural Formula 1, and in such a unit, the integer m may be 3 to 100 or greater than 100.
- MDI methylenediphenyl diisocyanate
- PTMG polytetramethylene glycol
- the elastic antibacterial polyurethane polymer may further include a unit derived from a diamine compound.
- the elastic antibacterial polyurethane polymer is (A) an isocyanate compound; (B) a polyol containing polyether glycol and a diol represented by Formula 1 below; and (C) a unit derived from a diamine compound. More specifically, (A) an isocyanate compound; And (B) the elastic antibacterial polyurethane polymer may be prepared by further reacting a diamine compound with a polymer (eg, a prepolymer) of a polyol including polyether glycol and a diol represented by Formula 1 below.
- a polymer eg, a prepolymer
- the diamine compound can function as a so-called chain extender.
- the type of diamine that can be used is not particularly limited, but, for example, ethylenediamine, 1,2'-propylenediamine, hexamethylene diamine, xylenediamine, 4, Compounds such as 4,4'-diphenylmethane diamine or hydrazine may be used in this application. Alternatively, one or more of the compounds listed above may be used.
- the molar ratio of the (C) diamine compound to the polyol (B) may be less than 1.0.
- the molar ratio of the diamine compound (C) to the polyol (B) may be 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, or 0.4 or less.
- the lower limit may be, for example, 0.1 mol or more, 0.2 mol or more, 0.3 mol or more, or 0.4 mol or more.
- the polyurethane may have a molecular weight of 10,000 or more. Specifically, the polyurethane may have a molecular weight of 50,000 or more or 100,000 or more. And, the upper limit may be, for example, 300,000 or less, 250,000 or less, 200,000 or less, 150,000 or less, or 100,000 or less. When the above-described range is satisfied, it may be advantageous to secure mechanical properties (eg, tensile properties), and in particular, exhibit elasticity in fiber applications.
- mechanical properties eg, tensile properties
- the antimicrobial elastomeric polyurethane polymer may exhibit certain properties.
- the polyurethane polymer of the present application may exhibit an antibacterial rate (bacteriostatic reduction rate) of 90% or more when measured according to JIS Z 2801.
- the antibacterial rate may be 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 99.9% or more.
- the polyurethane polymer may exhibit an antibacterial rate of substantially 100%. If the antibacterial rate is less than the above value, it is difficult to see that it has excellent antibacterial properties.
- the polyurethane polymer of the present application may have a thermal decomposition temperature (Td) of 280 °C or higher.
- Td thermal decomposition temperature
- the thermal decomposition temperature is, as in the experiment related to FIG. 1, when the weight loss of the polymer is evaluated while raising the temperature to 700 ° C. at a rate of 10 ° C./min under N 2 , the weight loss of the polymer ( weight loss) may mean the temperature (Td) (thermal decomposition start temperature) at the point when it becomes 10%.
- the thermal decomposition temperature may be, for example, 285 °C or higher, 290 °C or higher, 295 °C or higher, 300 °C or higher, 305 °C or higher, or 310 °C or higher.
- the upper limit is, for example, 350 °C or less, 345 °C or less, 340 °C or less, 335 °C or less, 330 °C or less, 325 °C or less, 320 °C or less, 315 °C or less, 310 °C or less, 305 °C or less or 300 It may be below °C. Within the above range, the polymer may have excellent processability and heat resistance durability.
- the polyurethane polymer of the present application may have a tensile strain of 900% or more measured according to the ASTM D882 tensile test method.
- the tensile strain is, for example, the ratio of width and length (width: length) of 1: 1 to 100, 1: 1 to 50, 1: 1 to 30, or 1: 1 to 10 elastic antibacterial polyurethane polymer can be measured for the sample.
- the tensile strain is, for example, 910% or more, 920% or more, 930% or more, 940% or more, 950% or more, 960% or more, 970% or more, 980% or more, 990% or more, 1000% or more or 1010% or more.
- the upper limit is, for example, 1100% or less, 1090% or less, 1080% or less, 1070% or less, 1060% or less, 1050% or less, 1040% or less, 1030% or less, 1020% or less, 1010% or less, or 1000% may be below.
- the polymer of the present application can maintain a high tensile strain rate while introducing the diol of Formula 1 to secure antibacterial properties.
- the polyurethane polymer of the present application may have a tensile strength of 30 Mpa or more measured according to the ASTM D882 tensile test method.
- the tensile strength is, for example, the ratio of width and length (width: length) of 1: 1 to 100, 1: 1 to 50, 1: 1 to 30, or 1: 1 to 10 elastic antibacterial polyurethane polymer can be measured for the sample.
- the tensile strength may be, for example, 35 Mpa or more, 40 Mpa or more, 45 Mpa or more, 50 Mpa or more, 55 Mpa or more, or 60 Mpa or more.
- the upper limit may be, for example, 65 Mpa or less, 60 Mpa or less, 55 Mpa or less, 50 Mpa or less, 45 Mpa or less, 40 Mpa or less, or 35 Mpa or less.
- the polymer of the present application can maintain high tensile strength while introducing the diol of Formula 1 to secure antibacterial properties.
- the polyurethane polymer of the present application may have an unreacted diol content of 1,000 ppm or less based on the total amount of the polymer.
- the unreacted content may be confirmed using HPLC (High Performance Liquid Chromatography).
- the content of the unreacted diol represented by Formula 1 relative to the entire polymer is 950 ppm or less, 900 ppm or less, 850 ppm or less, 800 ppm or less, 750 ppm or less, 700 ppm or less, 650 ppm or less, 600 ppm or less, 550 ppm or less, 500 ppm or less, 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, 200 ppm or less, 150 ppm or less, 100 ppm or less, or 50 ppm or less.
- mechanical properties tensile properties
- the polyurethane polymer is not particularly limited.
- the polymer is used as a raw material for fibers (e.g., elastic yarns such as spandex), fabrics, clothing (e.g., underwear, swimwear, socks, etc.), paints, interior materials for vehicles, interior materials for vehicles, mattresses, or foams.
- fibers e.g., elastic yarns such as spandex
- clothing e.g., underwear, swimwear, socks, etc.
- paints interior materials for vehicles, interior materials for vehicles, mattresses, or foams.
- the present application is directed to a method of making a resilient antimicrobial polyurethane polymer. According to this method, elastic antibacterial polyurethane polymers of the above-described construction are produced.
- the manufacturing method (A) an isocyanate compound; and (B) a step (S1) of mixing and reacting polyether glycol with a polyol including a diol represented by Formula 1 below.
- the polyol (B) includes 0.01 to 40 mol% of the diol represented by Formula 1.
- R1 and R2 are each independently hydrogen, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, or an alkylthio group or an aryl group. is tigi,
- L1 and L2 each independently, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group;
- L3 is a direct bond, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group;
- A is an alkylene group having more than 6 carbon atoms
- X - means an anion
- the number of carbon atoms in Chemical Formula 1A may mean the number of carbon atoms in the main chain.
- the reaction may proceed at a temperature of 100 °C or less.
- diisocyanate may generate a dimer through a side reaction, which is an obstacle to polymer synthesis.
- the reaction temperature may be 95 °C or less, 90 °C or less, 85 °C or less, 80 °C or less, 75 °C or less, 70 °C or less, 65 °C or less, or 60 °C or less.
- the lower limit may be, for example, 50 °C or higher, 55 °C or higher, 60 °C or higher, 65 °C or higher, or 70 °C or higher.
- the reaction may be performed over several tens of minutes to several tens of hours. Specifically, the reaction may be performed for, for example, 30 minutes or more, 60 minutes or more, or 90 minutes or more. And the upper limit of the reaction time may be, for example, 30 hours or less, 25 hours or less, 20 hours or less, 15 hours or less, 10 hours or less, or 5 hours or less. Within the above time range, the molecular weight of the polymer may be appropriately controlled and the occurrence of side reactions may be controlled.
- the method further reacts (C) a diamine compound to a prepolymer obtained by reacting (A) an isocyanate compound and (B) a polyol containing a polyether glycol and a diol represented by Formula 1 below A step S2 may be further included.
- a diluted solution is prepared by diluting the prepolymer or its solution in a solvent.
- the type of solvent for preparing the diluted solution is not particularly limited, but, for example, DMAc (dimethylacetamide) may be used.
- the concentration of the diluted solution may be adjusted so that the content of the prepolymer in the range of about 10 to 40 or 20 to 30% by weight of the total weight of the diluted solution.
- a diamine compound is added to the prepolymer dilution solution prepared as described above.
- the temperature when the diamine compound is added to the prepolymer diluent may be adjusted to 10 ° C. or less, for example, about 0 to 4 ° C., so that a rapid reaction does not occur when the diamine compound is added.
- the reaction may be carried out for about several hours, for example, 1 to 2 hours.
- the antibacterial elastic polyurethane of the present application may be provided through the reaction of the diamine compound, which is a chain extender, with the prepolymer.
- the antibacterial elastic polyurethane prepared by the above-described method satisfies the above-described properties (eg, antibacterial rate, tensile strain, tensile strength, and unreacted diol content).
- the present application relates to engineering plastics including the antimicrobial elastic polyurethane polymer.
- the engineering plastics are, for example, plastics used as parts materials for industrial or industrial machines and instruments, and their specific uses are not particularly limited.
- the present application relates to an article comprising the antimicrobial elastic polyurethane polymer.
- the article may be a fiber (eg, elastic yarn such as spandex), fabric, clothing (eg, underwear, swimwear, socks, etc.), paint, vehicle interior material, mattress, or foams.
- the article may be a spandex fiber including the above-described antibacterial elastomer, a fabric or a garment including the fiber.
- the present application relates to a spinning composition (or spinning solution) for producing elastic yarn.
- the spinning composition includes at least the elastomer described above.
- the present application relates to a method for preparing the spinning composition (or spinning solution) for preparing the elastic yarn.
- the method includes all of the methods and processes for producing the above-described elastic antibacterial polyurethane polymer.
- the present application relates to an elastic yarn (eg, spandex) including the antimicrobial elastic polyurethane polymer.
- the elastic yarn includes the polyurethane polymer having the same characteristics as described above, antibacterial properties may be provided without deterioration in tensile properties or heat resistance durability. These elastic yarns can be used for sanitary or medical textiles.
- the type of elastic yarn is not particularly limited as it can be mono or multifilament.
- the fineness is also not particularly limited, and may be appropriately adjusted depending on the purpose for which the fiber is used.
- the present application relates to a method for manufacturing the elastic yarn. Specifically, the method includes preparing a spinning solution (S1) and spinning the spinning solution (S2).
- the step (S1) includes (A) mixing and reacting an isocyanate compound, and (B) a polyol containing polyether glycol and the diol represented by Formula 1 (S11); and (A) an isocyanate compound; and (B) further reacting (C) a diamine compound with a prepolymer obtained by reacting polyether glycol with a polyol containing the diol represented by Formula 1 (S12).
- the polyol (B) includes 0.01 to 40 mol% of the diol represented by Formula 1.
- the contents of preparing the elastic antibacterial polyurethane which is the main component of the spinning solution (eg, preparation of the prepolymer, reaction between the prepolymer and diamine, etc.) are the same as those described in the elastic antibacterial polyurethane and its manufacturing method. Since they are the same, we omit them.
- the spinning process for producing fibers is not particularly limited.
- a spinning device equipped with a spinneret may be used, and the temperature during spinning may be adjusted to a level of, for example, 200° C. or higher or 250° C. or higher.
- cooling by air or liquid eg, water or other solvent-containing liquid
- liquid e.g, water or other solvent-containing liquid
- the method may further include winding (S3).
- the fiber cooled after spinning or spinning may be wound through a known method or device such as a winding roller.
- polyurethane having excellent antibacterial properties, mechanical properties (eg, tensile strength and tensile strain) and heat resistance can be provided.
- FIG. 1 is a graph showing experimental results regarding heat resistance. Specifically, FIG. 1A relates to Comparative Example 1, FIG. 1B relates to Example 1, and FIG. 1C relates to Example 2.
- MDI methylene diphenyl diisocyanate
- PTMG Poly (tetramethylene ether) glycol
- Mw molecular weight 2000.0 52.3 g
- quaternary ammonium diol having the structure of [Formula 1-1] below (Mw molecular weight 368.00 ) 1.1 g was introduced into the reactor, and the inside of the reactor was substituted with N 2 . Thereafter, a DMAc solvent was introduced into the reactor, and the temperature of the reactor was raised to 90° C., and the reaction proceeded for 90 minutes to prepare a polyurethane prepolymer.
- the prepared polyurethane prepolymer solution was mixed with a DMAc solvent to prepare a prepolymer solution diluted to a concentration of about 25% by weight, and 0.9 g of ethylene diamine (Mw molecular weight 60.10) within a temperature range of about 0 to 4 ° C. was added. Thereafter, after adding ethylene diamine, the reaction proceeded for about 1.5 hours, and a polyurethane polymer was prepared.
- ethylene diamine Mw molecular weight 60.10
- MDI methylene diphenyl diisocyanate
- PTMG Poly (tetramethylene ether) glycol
- Mw molecular weight 2000.0 53.3 g
- quaternary ammonium diol having the structure of [Formula 1-1] (Mw molecular weight 368.00 ) 0.5 g and 0.9 g of ethylene diamine (Mw molecular weight 60.10) were added into the reactor, and polyurethane was prepared in the same manner as in Example 1.
- MDI Methylene diphenyl diisocyanate
- PTMG Poly (tetramethylene ether) glycol
- Mw molecular weight 2000.0 54.0 g
- quaternary ammonium diol having the structure of [Formula 1-1] (Mw molecular weight 368.00 ) 0.1 g and 0.9 g of ethylene diamine (Mw molecular weight 60.10) were added into the reactor, and polyurethane was prepared in the same manner as in Example 1.
- Polyurethane was prepared using the same contents of PTMG, MDI and [Formula 1-1] as those used in Example 3. However, unlike Example 3 in which PTMG, MDI and [Formula 1-1] are reacted together, PTMG and MDI are reacted first (reacted until the reaction rate of NCO of MDI reaches about 99%), and the [ Chemical Formula 1-1] was introduced into the chain extender to react with the remaining -NCO groups.
- MDI polyol polyol PTMG Formula 1-1 Example 1 1.60 1.00 0.90 0.10
- Example 2 1.60 1.00 0.95 0.05
- the molar ratio between MDI and polyol was calculated by dividing the number of moles of isocyanate compound by the total number of moles of polyol.
- the ratio of the number of moles of PTMG or Chemical Formula 1-1 in the polyol which means mol% when expressed as a % ratio.
- the remaining monomer of Chemical Formula 1-1 in the polyurethane was quantitatively measured using an HPLC (High Performance Liquid Chromatography) analysis device. More specifically, first, the prepared resin pellets are put in a certain amount of solvent (saline), stirred for 24 hours, and then the extract is filtered to extract unreacted components in the resin. After taking the solution thus obtained, HPLC analysis was performed, and the components of the compound of Formula 1 remaining in the resin were measured by comparing with the previously measured HPLC analysis result of the copolymer monomer. In view of the experimental results described later, the remaining unreacted monomer of Chemical Formula 1-1 in the polymerized polyurethane is determined to be a cause of deterioration in mechanical properties.
- HPLC High Performance Liquid Chromatography
- Example 1-3 The antimicrobial activity of each polymer of Example 1-3 and Comparative Example 1-2 was evaluated. Specifically, a film (5 cm x 5 cm) was prepared by solvent casting a polymerization solution having a concentration of 20 wt% prepared using DMF (dimethylformamide) as a solvent, and antibacterial evaluation was performed according to the JIS Z2801 method.
- DMF dimethylformamide
- Examples 1-2 and Comparative Examples The heat resistance of each polymer was evaluated. Specifically, while raising the temperature to 700 °C at a rate of 10 °C/min under N 2 , the weight loss of the polymers was compared. The results are shown in FIGS. 1A (Comparative Example 1), 1B (Example 1) and 1C (Example 2).
- Example 1-3 The tensile properties of each polymer of Example 1-3 and Comparative Example 1-2 were evaluated. Specifically, the tensile strength and tensile strain of the sample were measured according to the tensile test method of ASTM D882.
- ASTM D882 relates to a tensile test of a thin film (about less than 1 mm in thickness), and the size of the sample in the experiment for the present invention is 5 mm x 50 mm (width x length) (thickness: about 200 to 300 ⁇ m ).
- tensile strength means a maximum stress until a material is fractured by a tensile load, and is a value obtained by dividing the maximum load by the cross-sectional area of the material.
- tensile strain means the strain when the material is deformed by tensile stress. It is expressed as the ratio of the change in length from the initial length.
- Examples 1-3 have higher tensile strength than Comparative Examples 1-2. In the case of tensile strain, Examples 1-3, which additionally secured antibacterial properties, show tensile strain comparable to Comparative Example 1. That is, Example 1-3 shows good elasticity (even though Chemical Formula 1-1 was additionally reacted).
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Abstract
Description
MDI | 폴리올 | |||
폴리올 | PTMG | 화학식 1-1 | ||
실시예 1 | 1.60 | 1.00 | 0.90 | 0.10 |
실시예 2 | 1.60 | 1.00 | 0.95 | 0.05 |
실시예 3 | 1.60 | 1.00 | 0.99 | 0.01 |
비교예 1 | 1.49 | 1.00 | 1.00 | - |
비교예 2 | 1.60 | 1.00 | 0.99 | 0.01 |
* 단위 (1) MDI와 폴리올 간 몰 비로서, 이소시아네이트 화합물의 몰수를 폴리올의 전체 몰수로 나누어 계산하였다. (2) 폴리올 중 PTMG 또는 화학식 1-1이 이 차지하는 몰수의 비율로서, % 비율로 표현하면 몰%를 의미한다. |
화학식 1-1의 미반응량(ppm) |
E.Coli (ATCC 8739)에 대한 항균력 (%) | 인장강도(MPa) | 인장변형률(%) | |
실시예 1 | 648 | 100 | 34.8±1.26 | 976.6±24.83 |
실시예 2 | 330 | 100 | 61.2±1.28 | 934.2±24.8 |
실시예 3 | 272 | 100 | 54.8±5.02 | 986.6±30.93 |
비교예 1 | - | 0 | 29.9±1.32 | 1023.1±50.45 |
비교예 2 | 1,271 | 100 | 25.3±2.76 | 736.1±36.35 |
Claims (22)
- (A) 이소시아네이트 화합물; 및 (B) 폴리에테르글리콜과 하기 화학식 1로 표시되는 디올을 포함하는 폴리올 유래의 단위를 포함하고,상기 (B) 폴리올은 화학식 1로 표시되는 디올을 0.01 내지 40 몰% 포함하는,탄성 항균 폴리우레탄 중합체:[화학식 1](단, 상기 화학식 1에서,R1 및 R2는, 각각 독립적으로, 수소, 알킬기, 할로알킬기, 알케닐기, 알키닐기, 아릴기, 헤테로 아릴기, 아릴옥시기, 알콕시기, 지환족 구조, 헤테로 지환족 구조 또는 알킬티오기 또는 아릴티오기이고,L1 및 L2, 각각 독립적으로, 알킬렌기, 헤테로아킬렌기, 싸이클로알킬렌기, 아릴렌기 또는 헤테로아릴렌기이며,L3는 직접결합, 알킬렌기, 헤테로아킬렌기, 싸이클로알킬렌기, 아릴렌기 또는 헤테로아릴렌기이고,상기 A는 탄소수가 6 초과인 알킬렌기이며,X-는 음이온을 의미한다.)
- 제 1 항에 있어서,JIS Z 2801에 따른 측정시 90 % 이상의 항균율을 보이는,탄성 항균 폴리우레탄 중합체.
- 제 1 항에 있어서,ASTM D882 인장 시험법에 따라 측정된 인장변형률이 900 % 이상인,탄성 항균 폴리우레탄 중합체(단, 상기 인장변형률은 폭과 길이의 비(폭 : 길이)가 1 : 1 내지 100인 탄성 항균 폴리우레탄 중합체 시료에 대하여 측정한 것이다).
- 제 1 항에 있어서,ASTM D882 인장 시험법에 따라 측정된 인장강도가 30 Mpa 이상인,탄성 항균 폴리우레탄 중합체(단, 상기 인장강도는 폭과 길이의 비(폭 : 길이)가 1 : 1 내지 100인 탄성 항균 폴리우레탄 중합체 시료에 대하여 측정한 것이다).
- 제 1 항에 있어서,화학식 1로 표시되는 미반응 디올의 함량이 전체 중합체에 대하여 1,000 ppm 이하인,탄성 항균 폴리우레탄 중합체.
- 제 1 항에 있어서,상기 (B) 폴리올에 대한 (A) 이소시아네이트 화합물의 몰비가 1.0 내지 2.0 범위인,탄성 항균 폴리우레탄 중합체.
- 제 1 항에 있어서,상기 A는 탄소수가 6 초과 20 이하의 알킬렌기인,탄성 항균 폴리우레탄 중합체.
- 제 1 항에 있어서,상기 X-는 F-, Cl-, Br-, I-, NO3 -, (CN)2N-, BF4 -, ClO4 -, RSO3 - (여기서, R은 탄소수 1-9의 알킬기 또는 페닐기), RCOO- (여기서, R은 탄소수 1-9의 알킬기 또는 페닐기), PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, (CF3SO3 -)2, (CF2CF2SO3 -)2, (C2F5SO2)2N-, (CF3SO3)2N-, (CF3SO2)(CF3CO)N-, CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3COO-, C3F7COO-, CF3SO3 -, 또는 C4F9SO3 - 인,탄성 항균 폴리우레탄 중합체.
- 제 1 항에 있어서,사슬 연장제인 (C) 디아민 화합물 유래의 단위를 더 포함하는,탄성 항균 폴리우레탄 중합체.
- (A) 이소시아네이트 화합물, 및 (B) 폴리에테르글리콜과 하기 화학식 1로 표시되는 디올을 포함하는 폴리올을 반응시키는 단계를 포함하고,상기 (B) 폴리올은 화학식 1로 표시되는 디올을 0.01 내지 40 몰% 포함하는,탄성 항균 폴리우레탄 중합체의 제조방법:[화학식 1](상기 화학식 1에서,R1 및 R2는, 각각 독립적으로, 수소, 알킬기, 할로알킬기, 알케닐기, 알키닐기, 아릴기, 헤테로 아릴기, 아릴옥시기, 알콕시기, 지환족 구조, 헤테로 지환족 구조 또는 알킬티오기 또는 아릴티오기이고,L1 및 L2, 각각 독립적으로, 알킬렌기, 헤테로아킬렌기, 싸이클로알킬렌기, 아릴렌기 또는 헤테로아릴렌기이며,L3는 직접결합, 알킬렌기, 헤테로아킬렌기, 싸이클로알킬렌기, 아릴렌기 또는 헤테로아릴렌기이고,상기 A는 탄소수가 6 초과인 알킬렌기이며,X-는 음이온을 의미한다.)
- 제 11 항에 있어서,상기 (B) 폴리올에 대한 상기 (A) 이소시아네이트 화합물의 몰비가 1.0 내지 2.0 범위가 되도록 상기 (B) 폴리올과 상기 (A) 이소시아네이트 화합물을 혼합하고 반응시키는,탄성 항균 폴리우레탄 중합체의 제조방법.
- 제 11 항에 있어서,상기 반응을 100 ℃ 이하의 온도에서 진행하는,탄성 항균 폴리우레탄 중합체의 제조방법.
- 제 11 항에 있어서,상기 A는 탄소수가 6 초과 20 이하의 알킬렌기인,탄성 항균 폴리우레탄 중합체의 제조방법.
- 제 11 항에 있어서,상기 X-는 F-, Cl-, Br-, I-, NO3 -, (CN)2N-, BF4 -, ClO4 -, RSO3 - (여기서, R은 탄소수 1-9의 알킬기 또는 페닐기), RCOO- (여기서, R은 탄소수 1-9의 알킬기 또는 페닐기), PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, (CF3SO3 -)2, (CF2CF2SO3 -)2, (C2F5SO2)2N-, (CF3SO3)2N-, (CF3SO2)(CF3CO)N-, CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3COO-, C3F7COO-, CF3SO3 -, 또는 C4F9SO3 - 인, 탄성 항균 폴리우레탄 중합체의 제조방법.
- 제 11 항에 있어서,(A) 이소시아네이트 화합물; 및 (B) 폴리에테르글리콜과 하기 화학식 1로 표시되는 디올을 포함하는 폴리올을 반응시켜 얻어진 프리폴리머(prepolymer)에 사슬 연장제인 (C) 디아민 화합물을 추가 반응시키는 단계를 더 포함하는, 탄성 항균 폴리우레탄 중합체의 제조방법.
- 제 11 항에 있어서,상기 탄성 항균 폴리우레탄 중합체는 JIS Z 2801에 따른 측정시 90 % 이상의 항균율을 보이는,탄성 항균 폴리우레탄 중합체의 제조방법.
- 제 11 항에 있어서,상기 탄성 항균 폴리우레탄 중합체는 ASTM D882 인장 시험법에 따라 측정된 인장변형률이 900 % 이상인,탄성 항균 폴리우레탄 중합체의 제조방법(단, 상기 인장변형률은 폭과 길이의 비(폭 : 길이)가 1 : 1 내지 100인 탄성 항균 폴리우레탄 중합체 시료에 대하여 측정한 것이다).
- 제 11 항에 있어서,상기 탄성 항균 폴리우레탄 중합체는 ASTM D882 인장 시험법에 따라 측정된 인장강도가 30 Mpa 이상인,탄성 항균 폴리우레탄 중합체의 제조방법(단, 상기 인장강도는 폭과 길이의 비(폭 : 길이)가 1 : 1 내지 100인 탄성 항균 폴리우레탄 중합체 시료에 대하여 측정한 것이다).
- 제 11 항에 있어서,상기 탄성 항균 폴리우레탄 중합체는 화학식 1로 표시되는 미반응 디올의 함량이 전체 중합체에 대하여 1,000 ppm 이하인,탄성 항균 폴리우레탄 중합체의 제조방법
- 제 1 항에 따른 폴리우레탄 중합체를 포함하는 물품이고,상기 물품은 섬유, 직물, 의복, 페인트, 차량용 내장재, 차량용 내장재, 매트리스 또는 발포체(foams)인, 물품.
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US5250649A (en) * | 1990-06-29 | 1993-10-05 | Becton, Dickinson And Company | Melt processable polyurethaneurea copolymers and method for their preparation |
US20120015574A1 (en) * | 2009-03-27 | 2012-01-19 | Carl Freudenberg Kg | Method for formulating a reactive polyurethane emulsion |
KR20130122622A (ko) * | 2010-10-19 | 2013-11-07 | 도레이 오페론텍스 가부시키가이샤 | 폴리우레탄 탄성사 및 그 제조 방법 |
US20180146665A1 (en) * | 2016-11-28 | 2018-05-31 | Aleo Bme, Inc. | Clickable antimicrobial molecules and polymers |
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US5250649A (en) * | 1990-06-29 | 1993-10-05 | Becton, Dickinson And Company | Melt processable polyurethaneurea copolymers and method for their preparation |
US20120015574A1 (en) * | 2009-03-27 | 2012-01-19 | Carl Freudenberg Kg | Method for formulating a reactive polyurethane emulsion |
KR20130122622A (ko) * | 2010-10-19 | 2013-11-07 | 도레이 오페론텍스 가부시키가이샤 | 폴리우레탄 탄성사 및 그 제조 방법 |
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