CN107141439A - A kind of antimicrobial form castor oil-base cation aqueous polyurethane emulsion and preparation method thereof - Google Patents
A kind of antimicrobial form castor oil-base cation aqueous polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN107141439A CN107141439A CN201710413261.XA CN201710413261A CN107141439A CN 107141439 A CN107141439 A CN 107141439A CN 201710413261 A CN201710413261 A CN 201710413261A CN 107141439 A CN107141439 A CN 107141439A
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- China
- Prior art keywords
- castor oil
- aqueous polyurethane
- polyurethane emulsion
- base
- base cation
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- 239000000839 emulsion Substances 0.000 title claims abstract description 78
- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 65
- 235000004443 Ricinus communis Nutrition 0.000 title claims abstract description 64
- 150000001768 cations Chemical class 0.000 title claims abstract description 52
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000004945 emulsification Methods 0.000 title claims abstract description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000004359 castor oil Substances 0.000 claims abstract description 40
- 235000019438 castor oil Nutrition 0.000 claims abstract description 40
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000004970 Chain extender Substances 0.000 claims abstract description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims abstract description 14
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 13
- 150000003384 small molecules Chemical group 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000010008 shearing Methods 0.000 claims abstract description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 230000000844 anti-bacterial effect Effects 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 description 18
- 241000191967 Staphylococcus aureus Species 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002362 mulch Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 timber processing Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 210000002429 large intestine Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Plant Pathology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of antimicrobial form castor oil-base cation aqueous polyurethane emulsion and preparation method thereof.A kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion, it is characterised in that obtained by following steps：(1) PEPA, castor oil, aliphatic diisocyanate, catalyst and small molecule chain extender are added and reacted in reactor；(2) reacted after adding cationic hydrophilic chain extender；(3) nertralizer is added into above-mentioned castor oil-base cation aqueous polyurethane prepolymer, adds deionized water after reaction thereto and carry out high speed shearing emulsification, remove after butanone, obtain castor oil-base aqueous polyurethane emulsion；(4) nano titanium oxide dispersion is added into above-mentioned castor oil-base aqueous polyurethane emulsion, ultrasonic disperse obtains antimicrobial form castor oil-base cation aqueous polyurethane emulsion.Present invention process flow is simple, environmental protection, and gained emulsion antibiotic property is strong, available for fields such as the antibiotic finishes of fabric.
Description
Technical field
The present invention relates to a kind of antimicrobial form castor oil-base cation aqueous polyurethane emulsion and preparation method thereof, belong to fine
High polymer material and its preparation field.
Background technology
Aqueous polyurethane (WPU) is one kind in high molecular synthetic material, the resistance to high/low warm nature of its film, wearability, resistance to
The performance such as corrosivity and pliability is more excellent, is mainly used in textile finishing, leather processing, coating, timber processing, building materials, papermaking
With the industry such as adhesive, it has the advantages that nontoxic, environmentally friendly and non-ignitable using water as decentralized medium.
Cation aqueous polyurethane has excellent performance, right due to containing positively charged quaternary ammonium salt group in molecule
Negatively charged cotton fiber has preferable affinity, easily with the hydroxyl formation hydrogen bond in cellulose so that fabric has after arrangement
There is preferable durability；Simultaneously because the presence of quaternary ammonium salt group, cation polyurethane has certain antibacterial action, but antibacterial
Species is less, and antibacterial ability is weaker.
Nano titanium oxide is conventional nano modified material, with photocatalysis, can be by the harmful substance in environment point
Solution is into innocuous substance, by most attention in terms of the depollution of environment.Nano TiO 2 is to Pseudomonas aeruginosa, large intestine bar according to the literature
Bacterium, staphylococcus aureus, salmonella, bud branch bacterium and aspergillus etc. have very strong killing ability, can be assigned for leather finish
Leather antibacterial is given, while nano titanium oxide has very strong ultraviolet radiation absorption function, sun care preparations and work(is widely used in
Energy coating etc., this is easy to be yellowing under solar radiation to solving leather coating, and improving its performance has important
Meaning.
Composite, synergic nano titanium dioxide and cationic water are carried out using nano titanium oxide and cation polyurethane
The advantage of property polyurethane, the anti-microbial property and mechanical property of cation aqueous polyurethane can be improved simultaneously, can preferably be answered
The fields such as the antibiotic finish for fabric.
The content of the invention
It is an object of the invention to provide a kind of antimicrobial form castor oil-base cation aqueous polyurethane emulsion and preparation method thereof,
This method technique is simple, environmental protection, emulsion anti-microbial property are excellent.
To achieve the above object, the technical solution used in the present invention is that a kind of antimicrobial form castor oil-base is cation water-based
Polyaminoester emulsion, it is characterised in that obtained by following steps：
(1) PEPA, castor oil, aliphatic diisocyanate, catalyst and small molecule chain extender are added and reacted
Reacted in device, obtain polyurethane based on castor oil oligomer；
(2) reacted after adding cationic hydrophilic chain extender into above-mentioned polyurethane based on castor oil oligomer, plus
Butanone adjusts viscosity to 16.0mPas-30.8mPas, obtains castor oil-base cation aqueous polyurethane prepolymer；
(3) nertralizer is added into above-mentioned castor oil-base cation aqueous polyurethane prepolymer, is added thereto after reaction
Deionized water carries out high speed shearing emulsification, removes after butanone, obtains castor oil-base aqueous polyurethane emulsion；
(4) nano titanium oxide dispersion is added into above-mentioned castor oil-base aqueous polyurethane emulsion, ultrasonic disperse is obtained
Antimicrobial form castor oil-base cation aqueous polyurethane emulsion (or antibacterial nano titanium dioxide cation aqueous polyurethane is compound
Emulsion).
A kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion, it is characterised in that including following step
Suddenly：
(1) PEPA, castor oil, aliphatic diisocyanate, catalyst and small molecule chain extender are added and reacted
Reacted in device, obtain polyurethane based on castor oil oligomer；
(2) reacted after adding cationic hydrophilic chain extender into above-mentioned polyurethane based on castor oil oligomer, plus
Butanone adjusts viscosity to 16.0mPas-30.8mPas, obtains castor oil-base cation aqueous polyurethane prepolymer；
(3) nertralizer is added into above-mentioned castor oil-base cation aqueous polyurethane prepolymer, is added thereto after reaction
Deionized water carries out high speed shearing emulsification, removes after butanone and (removes butanone using vacuum distillation), obtains castor oil-base aqueous poly-
Urethane emulsion；
(4) nano titanium oxide dispersion is added into above-mentioned castor oil-base aqueous polyurethane emulsion, ultrasonic disperse is obtained
Antimicrobial form castor oil-base cation aqueous polyurethane emulsion (or antibacterial nano titanium dioxide cation aqueous polyurethane is compound
Emulsion).In above-mentioned preparation method, step (1) reaction needs in advance castor oil and PEPA to be carried out removing water process,
1.5h is removed water in reduced vacuum at 115 DEG C；Inert gas shielding, such as nitrogen are needed in course of reaction.
Step (1) described reaction temperature is 60 DEG C~80 DEG C, concretely 70 DEG C or 80 DEG C；Reaction time be 2.0h~
3.5h, concretely 2.0h or 3.0h；Inert gas shielding (such as nitrogen or argon gas) is needed in course of reaction.
In step (1), PEPA, castor oil, diisocyanate, catalyst, small molecule chain extender account for for consumption
Always the proportion of resin quality is respectively：25%~45%；5%~20%；31.6%~45.6%；0.028%-0.072%；
1%~4%；Specifically, PEPA accounting can be 30.7% or 39.7%；Castor oil accounting can for 5.7% or
16.8%；Aliphatic diisocyanate accounting can be 34% or 37%；Small molecule chain extender accounting can be 2% or 3%；Step
(2) in, by the consumption of cationic hydrophilic chain extender account for total resin quality proportion be 6%~12%, concretely 6% or
8%；Total resin quality be PEPA, castor oil, aliphatic diisocyanate, catalyst, small molecule chain extender and
Cationic hydrophilic chain extender quality sum.
Step (1) described PEPA is in poly-epsilon-caprolactone, polyethylene glycol adipate, PCDL
One or more press the mixing of any proportioning；
Step (1) described aliphatic diisocyanate is dicyclohexyl methyl hydride -4,4- diisocyanate, 2,2,4- trimethyls
One or more in hexamethylene diisocyanate, IPDI press the mixing of any proportioning；
Catalyst described in step (1) is dibutyl tin dilaurate；
Small molecule chain extender described in step (1) is that one or both of ethylene glycol, BDO arbitrary proportion is mixed
Close.
Cationic hydrophilic chain extender described in step (2) is in N methyldiethanol amine, diethanol amine, triethanolamine
One kind；The feed postition of step (2) cationic hydrophilic chain extender is to be added dropwise dropwise.
Step (2) described reaction temperature is 40 DEG C~60 DEG C, concretely 45 DEG C or 55 DEG C；Reaction time be 1.5h~
3.0h, concretely 1.5h or 2.0h.
In above-mentioned preparation method, in step (3), by degree of neutralization be 100%, solid content be 25wt% determine nertralizer and
The quality of deionized water；
Nertralizer described in step (3) is glacial acetic acid.
It is 0.5h~1.0h that deionized water is added in step (3) and carries out time of emulsification pretreatment, concretely 0.5h or
1.0h。
Add the mode of deionized water in step (3) to be added portionwise, wherein, it is added dropwise dropwise before system phase reversal.
In above-mentioned preparation method, the consumption of the nano titanium oxide in step (4) in nano titanium oxide dispersion is accounted for
The 0.5%~2% of castor oil-base aqueous polyurethane emulsion quality, concretely 0.5% or 1.5%；Nano-silica in step (4)
It is 1: 20 preparation to change titanium dispersion liquid according to nano titanium oxide and absolute ethyl alcohol mass ratio.
The ultrasonic disperse time is 0.5h~1.0h in step (4), concretely 0.5h or 1.0h.
The antimicrobial form castor oil-base cation aqueous polyurethane emulsion of the present invention can be applicable to water paint and antimicrobial form is knitted
In thing finishing agent.
The present invention has advantages below：
(1) some polyesters polyalcohol is substituted with biomass material castor oil, it is possible to reduce the use of petrochemical material.
(2) hydroxyl value of castor oil is about 163mKOH/g, and hydroxyl average functionality is 2.7, it is possible to reduce or avoid using small
Molecule cross-link agent, while can assign film excellent mechanical property.
(3) the composite modified cation polyurethane of nano titanium oxide is used, is strengthening the anti-microbial property of cation polyurethane
Meanwhile, also improve the tensile strength of cation polyurethane.
(4) this method technique is simple, environmental protection, emulsion anti-microbial property are excellent.
Embodiment
Further detailed description is done to the present invention with reference to embodiment, but the implementation of the present invention is not limited to this.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used in following embodiments etc. unless otherwise specified, are commercially obtained.
Nano titanium oxide dispersion is 1: 20 according to nano titanium oxide and absolute ethyl alcohol mass ratio in following embodiments
Prepare.
The preparation of the antimicrobial form castor oil-base cation aqueous polyurethane emulsion of embodiment 1
Polyethylene glycol adipate (PBA-1000) 9.7g, castor oil (CO) 5.3g are added into (wherein, PBA- in reactor
1000 30.7%, the CO for accounting for total resin quality account for total resin quality 16.8%), at 115 DEG C reduced vacuum remove water 1.5h, treat
System temperature adds IPDI (IPDI) 12.2g and dibutyl tin laurate (DBTDL) 2 when being down to 60 DEG C
Drip (about 0.01-0.02g, same as below), R values are 1.2, system 80 DEG C of insulation reaction 2h under nitrogen atmosphere.Then to system
Middle addition BDO (BDO) 0.6g, continues insulation reaction 1h at 80 DEG C.
System is cooled to 55 DEG C, N methyldiethanol amine (MDEA) 2.5g (MDEA accounts for the 8% of total resin quality) is added dropwise,
Insulation reaction 1.5h, adds 4.0g butanone, agitation and dilution regulation system viscosity (viscosity is 30.8mPas).
System is cooled to 35 DEG C, 1.3g glacial acetic acid neutralization reactions 0.5h (degree of neutralization is 100%) is added, 95g is added and goes
Ionized water (solid content is 25wt%), high speed shearing emulsification 0.5h, vacuum distillation removing butanone (MEK) obtains castor oil-base water
Property polyaminoester emulsion, then, add nano titanium oxide dispersion (nano titanium oxide dispersion according to nano titanium oxide with
Absolute ethyl alcohol mass ratio is to prepare at 1: 20, same as below), the consumption of the nano titanium oxide in nano titanium oxide dispersion is
0.6g, the consumption of nano titanium oxide accounts for the 0.5% of castor oil-base aqueous polyurethane emulsion quality, ultrasonic disperse 0.5h, obtains
Antimicrobial form castor oil-base cation aqueous polyurethane emulsion, solid content is 25% (quality, same as below).
Gained emulsion is 91.5% (examination criteria is ASTM E2315-03) to the bacteriostasis rate of staphylococcus aureus, is said
Bright emulsion anti-microbial property of the present invention is excellent.By emulsion plastic film mulch, the tensile strength of gained film is 22.3MPa, and elongation at break is
306.7%.
The preparation of embodiment 2, antimicrobial form castor oil-base cation aqueous polyurethane emulsion
Polyethylene glycol adipate (PBA-1000) 9.3g, castor oil (CO) 5.7g are added into (wherein, PBA- in reactor
1000 30.7%, the CO for accounting for total resin quality account for total resin quality 16.8%), at 115 DEG C reduced vacuum remove water 1.5h, treat
System temperature adds IPDI (IPDI) 13.8g and dibutyl tin laurate (DBTDL) 2 when being down to 60 DEG C
Drop, R values are 1.2, system 80 DEG C of insulation reaction 2h under nitrogen atmosphere.Then to addition BDO (BDO) in system
1.0g, continues insulation reaction 1h at 80 DEG C.
System is cooled to 45 DEG C, N methyldiethanol amine (MDEA) 2.7g (MDEA accounts for the 8% of total resin quality) is added dropwise,
Insulation reaction 2.0h, adds 4.0g butanone, agitation and dilution regulation system viscosity (viscosity is 30.8mPas).
System is cooled to 35 DEG C, 1.4g glacial acetic acid neutralization reactions 0.5h (degree of neutralization is 100%) is added, 102g is added and goes
Ionized water (solid content is 25wt%), high speed shearing emulsification 1.0h, vacuum distillation removing butanone (MEK) then, adds 0.6g and received
(0.6g herein is the quality of nano titanium oxide in dispersion liquid to rice titanium oxide dispersion, and the consumption of nano titanium oxide is accounted for
Castor oil-base aqueous polyurethane emulsion quality 0.5%), ultrasonic disperse 0.5h obtains antimicrobial form castor oil-base cation water-based
Polyaminoester emulsion, solid content is 25%.
Gained emulsion is 91.0% (examination criteria is ASTM E2315-03) to the bacteriostasis rate of staphylococcus aureus, is said
Bright emulsion anti-microbial property of the present invention is excellent.By emulsion plastic film mulch, the tensile strength of gained film is 28.5MPa, and elongation at break is
254.3%.
The preparation of embodiment 3, antimicrobial form castor oil-base cation aqueous polyurethane emulsion
PCDL (PCDL-1000) 9.7g, castor oil (CO) 5.3g are added into (wherein, PCDL- in reactor
1000 30.7%, the CO for accounting for total resin quality account for total resin quality 16.8%), at 115 DEG C reduced vacuum remove water 1.5h, treat
System temperature adds dicyclohexyl methyl hydride -4,4- diisocyanate (HMDI) 14.4g and di lauric dibutyl when being down to 60 DEG C
Tin (DBTDL) 2 drips, and R values are 1.2, system 70 DEG C of insulation reaction 3h under nitrogen atmosphere.Then to adding ethylene glycol in system
(EG) 0.4g, insulation continues to react 1h at 80 DEG C.
System is cooled to 55 DEG C, N methyldiethanol amine (MDEA) 2.5g (MDEA accounts for the 8% of total resin quality) is added dropwise,
Insulation reaction 1.5h, adds 4.0g butanone, agitation and dilution regulation system viscosity (viscosity is 30.8mPas).
System is cooled to 35 DEG C, 1.3g glacial acetic acid neutralization reactions 0.5h (degree of neutralization is 100%) is added, 95g is added and goes
Ionized water (solid content is 25wt%), high speed shearing emulsification 0.5h, vacuum distillation removing butanone (MEK) then, adds 2.0g and received
(2.0g herein is the quality of nano titanium oxide in dispersion liquid to rice titanium oxide dispersion, and the consumption of nano titanium oxide is accounted for
Castor oil-base aqueous polyurethane emulsion quality 1.5%), ultrasonic disperse 1.0h obtains antimicrobial form castor oil-base cation water-based
Polyaminoester emulsion, solid content is 25%.
Gained emulsion is 97.2% (examination criteria is ASTM E2315-03) to the bacteriostasis rate of staphylococcus aureus, is said
Bright emulsion anti-microbial property of the present invention is excellent.By emulsion plastic film mulch, the tensile strength of gained film is 29.2MPa, and elongation at break is
251.4%.
The preparation of embodiment 4, antimicrobial form castor oil-base cation aqueous polyurethane emulsion
(wherein, polyethylene glycol adipate (PBA-1000) 13.2g, castor oil (CO) 1.8g is added in reactor
PBA-1000 account for total resin quality 37.4%, CO account for total resin quality 5.7%), removed water in reduced vacuum at 115 DEG C
1.5h, adds IPDI (IPDI) 11.6g and dibutyl tin laurate when system temperature is down to 60 DEG C
(DBTDL) 2 drop, R values are 1.2, system 80 DEG C of insulation reaction 2h under nitrogen atmosphere.Then to adding BDO in system
(BDO) 0.6g, continues insulation reaction 1h at 80 DEG C.
System is cooled to 55 DEG C, N methyldiethanol amine (MDEA) 2.5g (MDEA accounts for the 8% of total resin quality) is added dropwise,
Insulation reaction 1.5h, adds 4.0g butanone, agitation and dilution regulation system viscosity (viscosity is 30.8mPas).
System is cooled to 35 DEG C, 1.2g glacial acetic acid neutralization reactions 0.5h (degree of neutralization is 100%) is added, 93g is added and goes
Ionized water (solid content is 25wt%), high speed shearing emulsification 0.5h, vacuum distillation removing butanone (MEK) then, adds 0.6g and received
(0.6g herein is the quality of nano titanium oxide in dispersion liquid to rice titanium oxide dispersion, and the consumption of nano titanium oxide is accounted for
Castor oil-base aqueous polyurethane emulsion quality 0.5%), ultrasonic disperse 0.5h obtains antimicrobial form castor oil-base cation water-based
Polyaminoester emulsion, solid content is 25%.
Gained emulsion is 89.4% (examination criteria is ASTM E2315-03) to the bacteriostasis rate of staphylococcus aureus, is said
Bright emulsion anti-microbial property of the present invention is excellent.By emulsion plastic film mulch, the tensile strength of gained film is 12.6MPa, and elongation at break is
382.8%.
The preparation of embodiment 5, antimicrobial form castor oil-base cation aqueous polyurethane emulsion
(wherein, polyethylene glycol adipate (PBA-1000) 13.1g, castor oil (CO) 1.9g is added in reactor
PBA-1000 account for total resin quality 39.7%, CO account for total resin quality 5.7%), removed water in reduced vacuum at 115 DEG C
1.5h, adds IPDI (IPDI) 13.1g and dibutyl tin laurate when system temperature is down to 60 DEG C
(DBTDL) 2 drop, R values are 1.2, system 75 DEG C of insulation reaction 2.5h under nitrogen atmosphere.Then to addition Isosorbide-5-Nitrae-fourth two in system
Alcohol (BDO) 1.0g, insulation continues to react 1h at 80 DEG C.
System is cooled to 55 DEG C, N methyldiethanol amine (MDEA) 2.6g (MDEA accounts for the 8% of total resin quality) is added dropwise,
Insulation reaction 1.5h, adds 4.0g butanone, agitation and dilution regulation system viscosity (viscosity is 30.8mPas).
System is cooled to 35 DEG C, 1.3g glacial acetic acid neutralization reactions 0.5h (degree of neutralization is 100%) is added, 99g is added and goes
Ionized water (solid content is 25wt%), high speed shearing emulsification 0.5h, vacuum distillation removing butanone (MEK) then, adds 1.3g and received
(1.3g herein is the quality of nano titanium oxide in dispersion liquid to rice titanium oxide dispersion, and the consumption of nano titanium oxide is accounted for
Castor oil-base aqueous polyurethane emulsion quality 1.5%), ultrasonic disperse 0.5h obtains antimicrobial form castor oil-base cation water-based
Polyaminoester emulsion, solid content is 25%.
Gained emulsion is 95.4% (examination criteria is ASTM E2315-03) to the bacteriostasis rate of staphylococcus aureus, is said
Bright emulsion anti-microbial property of the present invention is excellent.By emulsion plastic film mulch, the tensile strength of gained film is 20.8MPa, and elongation at break is
279.2.8%.
The preparation of embodiment 6, antimicrobial form castor oil-base cation aqueous polyurethane emulsion
(wherein, polyethylene glycol adipate (PBA-1000) 10.3g, castor oil (CO) 4.7g is added in reactor
PBA-1000 account for total resin quality 36.7%, CO account for total resin quality 16.8%), removed water in reduced vacuum at 115 DEG C
1.5h, adds IPDI (IPDI) 10.0g and dibutyl tin laurate when system temperature is down to 60 DEG C
(DBTDL) 2 drop, R values are 1.2, system 80 DEG C of insulation reaction 2h under nitrogen atmosphere.Then to adding BDO in system
(BDO) 0.6g, continues insulation reaction 1h at 80 DEG C.
System is cooled to 55 DEG C, N methyldiethanol amine (MDEA) 1.7g (MDEA accounts for the 6% of total resin quality) is added dropwise,
Insulation reaction 1.5h, adds 4.0g butanone, agitation and dilution regulation system viscosity (viscosity is 30.8mPas).
System is cooled to 35 DEG C, 0.9g glacial acetic acid neutralization reactions 0.5h (degree of neutralization is 100%) is added, 84g is added and goes
Ionized water (solid content is 25wt%), high speed shearing emulsification 0.5h, vacuum distillation removing butanone (MEK) then, adds 0.4g and received
(0.4g herein is the quality of nano titanium oxide in dispersion liquid to rice titanium oxide dispersion, and the consumption of nano titanium oxide is accounted for
Castor oil-base aqueous polyurethane emulsion quality 0.5%), ultrasonic disperse 0.5h obtains antimicrobial form castor oil-base cation water-based
Polyaminoester emulsion, solid content is 25%.
Gained emulsion is 87.8% (examination criteria is ASTM E2315-03) to the bacteriostasis rate of staphylococcus aureus, is said
Bright emulsion anti-microbial property of the present invention is excellent.By emulsion plastic film mulch, the tensile strength of gained film is 20.3MPa, and elongation at break is
346.2%.
Each raw material cited by the present invention, and each raw material of the invention bound, interval value, and technological parameter
The bound of (such as temperature, time), interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. a kind of antimicrobial form castor oil-base cation aqueous polyurethane emulsion, it is characterised in that obtained by following steps：
(1) PEPA, castor oil, aliphatic diisocyanate, catalyst and small molecule chain extender are added in reactor
Reacted, obtain polyurethane based on castor oil oligomer；
(2) reacted after adding cationic hydrophilic chain extender into above-mentioned polyurethane based on castor oil oligomer, plus butanone
Viscosity is adjusted to 16.0mPas-30.8mPas, castor oil-base cation aqueous polyurethane prepolymer is obtained；
(3) add nertralizer into above-mentioned castor oil-base cation aqueous polyurethane prepolymer, after reaction thereto add go from
Sub- water carries out high speed shearing emulsification, removes after butanone, obtains castor oil-base aqueous polyurethane emulsion；
(4) nano titanium oxide dispersion is added into above-mentioned castor oil-base aqueous polyurethane emulsion, ultrasonic disperse obtains antibacterial
Type castor oil-base cation aqueous polyurethane emulsion.
2. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion, it is characterised in that including following step
Suddenly：
(1) PEPA, castor oil, aliphatic diisocyanate, catalyst and small molecule chain extender are added in reactor
Reacted, obtain polyurethane based on castor oil oligomer；
(2) reacted after adding cationic hydrophilic chain extender into above-mentioned polyurethane based on castor oil oligomer, plus butanone
Viscosity is adjusted to 16.0mPas-30.8mPas, castor oil-base cation aqueous polyurethane prepolymer is obtained；
(3) add nertralizer into above-mentioned castor oil-base cation aqueous polyurethane prepolymer, after reaction thereto add go from
Sub- water carries out high speed shearing emulsification, removes after butanone, obtains castor oil-base aqueous polyurethane emulsion；
(4) nano titanium oxide dispersion is added into above-mentioned castor oil-base aqueous polyurethane emulsion, ultrasonic disperse obtains antibacterial
Type castor oil-base cation aqueous polyurethane emulsion.
3. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：Step (1) reaction needs in advance castor oil and PEPA to be carried out removing water process, in decompression at 115 DEG C
Vaccum dewatering 1.5h；Inert gas shielding is needed in course of reaction.
4. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：Step (1) described reaction temperature is 60 DEG C~80 DEG C；Reaction time is 2.0h~3.5h；Needed in course of reaction
Inert gas shielding.
5. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：In step (1), PEPA, castor oil, diisocyanate, catalyst, small molecule chain extender account for for consumption
Always the proportion of resin quality is respectively：25%~45%；5%~20%；31.6%~45.6%；0.028%-0.072%；
1%~4%；
In step (2), the proportion for accounting for total resin quality by the consumption of cationic hydrophilic chain extender is 6%~12%；
Total resin quality be PEPA, castor oil, aliphatic diisocyanate, catalyst, small molecule chain extender and
Cationic hydrophilic chain extender quality sum.
6. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2 or 5,
It is characterized in that：Step (1) described PEPA is poly-epsilon-caprolactone, polyethylene glycol adipate, PCDL
In one or more press any proportioning mixing；
Step (1) described aliphatic diisocyanate be dicyclohexyl methyl hydride -4,4- diisocyanate, 2,2,4- trimethyls oneself two
One or more in isocyanates, IPDI press the mixing of any proportioning；
Catalyst described in step (1) is dibutyl tin dilaurate；
Small molecule chain extender described in step (1) is the mixing of one or both of ethylene glycol, BDO arbitrary proportion.
Cationic hydrophilic chain extender described in step (2) is one in N methyldiethanol amine, diethanol amine, triethanolamine
Kind.
7. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：Step (2) described reaction temperature is 40 DEG C~60 DEG C；Reaction time is 1.5h~3.0h.
8. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：It is that 100%, solid content is the quality that 25wt% determines nertralizer and deionized water by degree of neutralization in step (3)；
Nertralizer described in step (3) is glacial acetic acid；
Deionized water is added in step (3) and carries out the time of emulsification pretreatment for 0.5h~1.0h.
9. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：The consumption of nano titanium oxide in step (4) in nano titanium oxide dispersion accounts for the aqueous poly- ammonia of castor oil-base
The 0.5%~2% of ester quality of the emulsion；Nano titanium oxide dispersion is according to nano titanium oxide and absolute ethyl alcohol in step (4)
Mass ratio is 1: 20 preparation.
10. a kind of preparation method of antimicrobial form castor oil-base cation aqueous polyurethane emulsion according to claim 2, its
It is characterised by：The ultrasonic disperse time is 0.5h~1.0h in step (4).
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