WO2024087584A1 - Diester-based gemini quaternary ammonium salt as well as preparation method therefor and use thereof - Google Patents
Diester-based gemini quaternary ammonium salt as well as preparation method therefor and use thereof Download PDFInfo
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- WO2024087584A1 WO2024087584A1 PCT/CN2023/093860 CN2023093860W WO2024087584A1 WO 2024087584 A1 WO2024087584 A1 WO 2024087584A1 CN 2023093860 W CN2023093860 W CN 2023093860W WO 2024087584 A1 WO2024087584 A1 WO 2024087584A1
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- WIPO (PCT)
- Prior art keywords
- acid
- quaternary ammonium
- diester
- ammonium salt
- reaction
- Prior art date
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 60
- 150000005690 diesters Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 ester amine Chemical class 0.000 claims description 42
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 26
- 239000004744 fabric Substances 0.000 claims description 24
- 239000011973 solid acid Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 20
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000005956 quaternization reaction Methods 0.000 claims description 14
- 229960002887 deanol Drugs 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000012972 dimethylethanolamine Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000004659 sterilization and disinfection Methods 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 5
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 17
- 239000002979 fabric softener Substances 0.000 abstract description 9
- 239000003599 detergent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000000047 product Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 20
- 238000006386 neutralization reaction Methods 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 11
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000005639 Lauric acid Substances 0.000 description 7
- 231100000460 acute oral toxicity Toxicity 0.000 description 7
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 241000222122 Candida albicans Species 0.000 description 4
- 206010040880 Skin irritation Diseases 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940095731 candida albicans Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000036556 skin irritation Effects 0.000 description 4
- 231100000475 skin irritation Toxicity 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 238000012449 Kunming mouse Methods 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 241000283977 Oryctolagus Species 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 208000005374 Poisoning Diseases 0.000 description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 231100000344 non-irritating Toxicity 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 208000024891 symptom Diseases 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N dodecanoic acid ethyl ester Natural products CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- 229940067592 ethyl palmitate Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N hexadecanoic acid ethyl ester Natural products CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N octadecanoic acid ethyl ester Natural products CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- YYZUSRORWSJGET-UHFFFAOYSA-N octanoic acid ethyl ester Natural products CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HUWNEIYHSQPEGW-UHFFFAOYSA-N azane;4,5-dihydro-1h-imidazole Chemical class N.C1CN=CN1 HUWNEIYHSQPEGW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
Definitions
- the invention relates to the technical field of cationic surfactants, and in particular to a diester-based Gemini quaternary ammonium salt and a preparation method and application thereof.
- fabric fibers After a period of use, fabric fibers usually become stiff and feel rough (especially cotton fabrics), which can cause a lot of inconvenience to users.
- the current common solution is to soften the fabric.
- Fabric softeners combine with the negative charge on the surface of fabric fibers through electrostatic attraction and adhere to their surface, which gives the fabric a softer and fluffy texture, helps reduce fabric wrinkles, and gives the fabric a pleasant fragrance.
- the main components of fabric softeners are mainly silicone surfactants and cationic surfactants quaternary ammonium salts.
- Quaternary ammonium salts mainly include: alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, diamide alkoxy ammonium salts and imidazoline ammonium salts.
- traditional fabric softener dialkyl quaternary ammonium salts (mainly D1821) have excellent fabric softness, but have poor biodegradability, easy to make fabric yellowing, poor compatibility, high production cost, and difficulty in preparing high-concentration products. In particular, they are more polluting to the environment. Since the 1990s, major European developed countries such as Germany have stopped using such products.
- ester quaternary ammonium salts mainly referring to di-long-chain ester quaternary ammonium salts
- D1821 poor biodegradability and easy yellowing of fabrics.
- ABS linear alkylbenzene sulfonate
- Gemini quaternary ammonium salts are dimeric amphiphilic molecules formed by connecting two monomeric quaternary ammonium salts through chemical bonds.
- the hydrophilic groups are connected by chemical bonds, which not only ensures the hydrophilic properties of the hydrophilic groups of Gemini quaternary ammonium salts, but also promotes close contact between molecules.
- dialkyl quaternary ammonium salts with the same hydrophobic chain Gemini quaternary ammonium salts have more Good water solubility and lower Krafft point.
- Gemini quaternary ammonium salts give them better surface/interfacial activity and application performance, and they have broad application prospects in the fields of sterilization and disinfection, fabric softening, tertiary oil recovery and metal corrosion inhibition.
- Liu Dantong et al. used palmitic acid, thionyl chloride, N,N-dimethylethanolamine and 1,4-dibromobutane as raw materials, and successfully synthesized butylene-based diester-based Gemini quaternary ammonium salts through acylation, esterification and quaternization reactions.
- the product has good re-wetting and anti-yellowing ability in fabric treatment, and adding a small amount of this product can give the fabric a soft feel.
- Niu Hua et al. used N, N-dimethylethanolamine and stearic acid as raw materials, synthesized dimethyl stearic acid ethyl ester tertiary amine intermediates through esterification reaction, and then synthesized a Gemini quaternary ammonium salt containing ester group through epoxy ring opening and quaternization reaction with octadecyl dimethyl tertiary amine, hydrochloric acid and epichlorohydrin and applied it in the field of fabric softening.
- the purpose of the present invention is to overcome the problems existing in the prior art and provide a diester-based Gemini quaternary ammonium salt and a preparation method and application thereof.
- the present invention provides a diester-based Gemini quaternary ammonium salt having the following structure:
- n 8, 10, 12, 14, 16, 18 or 20;
- R is CH 3 or CH 2 CH 3 ;
- X is HCOO, CH 3 COO, CH 3 CH 2 COO or CH 3 CH(OH)COO.
- the present invention also provides a method for preparing a diester-based Gemini quaternary ammonium salt, comprising the following steps:
- the fatty acid in step (1) has the following structure: n is 8, 10, 12, 14, 16, 18 or 20;
- the ethanolamine substance is dimethylethanolamine or diethylethanolamine
- the molar ratio of the fatty acid to the ethanolamine substance is 1:1.1-1.3.
- the solid acid catalyst in step (1) comprises a carrier and an active component
- the carrier is one or more of multi-level pore HY molecular sieve, multi-level pore HZSM-5 molecular sieve, SiO 2 , TiO 2 , ⁇ -Al 2 O 3 ;
- the active component is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, germanotungstic acid, germanomolybdic acid;
- the mass ratio of the active component to the solid acid catalyst is 5-25:100; the mass of the solid acid catalyst is 0.1-1.4wt% of the total mass of the fatty acid and the ethanolamine substances.
- the temperature of the esterification reaction in step (1) is 120-160° C.
- the time of the esterification reaction is 6-12 hours.
- the organic acid in step (2) is one or more of formic acid, acetic acid, propionic acid and lactic acid; and the solvent is one or more of water, ethanol, ethylene glycol, n-propanol, isopropanol and propylene glycol.
- the molar ratio of the monoalkyl ester amine intermediate, the organic acid and epichlorohydrin is 1.9-2.1:1.0-1.1:0.9-1.0; and the mass of the solvent is 39-60wt% of the sum of the mass of the monoalkyl ester amine intermediate, the organic acid, the solvent and epichlorohydrin.
- the temperature of the quaternization reaction in step (2) is 80 to 120° C.
- the time of the quaternization reaction is 4 to 16 hours.
- the invention also provides application of the diester-based Gemini quaternary ammonium salt in disinfection and sterilization or fabric softening.
- a heterogeneous supported catalyst is used to catalyze the esterification reaction, which has high reaction efficiency, good catalyst stability, and can be recycled and reused, thereby avoiding the residue of traditional homogeneous catalysts such as phosphorous acid in the product and ensuring the purity of the target product; an organic acid is used instead of traditional hydrochloric acid as an acid-base neutralizer to avoid the corrosion of hydrochloric acid to the production equipment, and the production equipment requirements are simple and the working environment is relatively safe.
- the product prepared by the present invention is a new type of diester-based Gemini quaternary ammonium salt containing organic acid counterions.
- the low chloride ion content makes it basically non-corrosive to metal equipment in practical applications; the product has good water solubility, good biodegradability, and the characteristics of low toxicity and low irritation.
- It has obvious advantages over traditional alkyl quaternary ammonium salts in the fields of disinfection, sterilization, fabric softening, etc., and can be used for disinfection of public places, skin and mucous membranes; it has the characteristics of high bactericidal efficiency and a wide antibacterial spectrum, and is used as the main component of a fabric softener.
- the fabric softening is comparable to that of traditional D1821 and ester-based quaternary ammonium salts; and the product has excellent compatibility with anionic and nonionic surfactants, and can be used as the main component of an antibacterial detergent.
- the product prepared by the present invention showed no obvious poisoning symptoms or death in all the test animals during the 14-day observation period.
- the acute oral toxicity LD50 of the sample to SPF-grade KM mice was greater than 5000 mg/kg ⁇ BW, which is practically non-toxic.
- the primary biodegradability of the sample on the seventh day was as high as 99%, which can be defined as a "green surfactant". It showed excellent antibacterial properties against Staphylococcus aureus, Escherichia coli, Candida albicans and Pseudomonas aeruginosa (antibacterial logarithm value > 5).
- the softness was better than that of ester-based quaternary ammonium salts, and the special hydrophilic head group structure made the product have better water solubility than ester-based quaternary ammonium salts, and the actual application effect was better.
- the present invention provides a diester-based Gemini quaternary ammonium salt having the following structure:
- n 8, 10, 12, 14, 16, 18 or 20;
- R is CH 3 or CH 2 CH 3 ;
- X is HCOO, CH 3 COO, CH 3 CH 2 COO or CH 3 CH(OH)COO.
- the present invention also provides a method for preparing a diester-based Gemini quaternary ammonium salt, comprising the following steps:
- the fatty acid in step (1) has the following structure: n is 8, 10, 12, 14, 16, 18 or 20;
- the ethanolamine substance is dimethylethanolamine or diethylethanolamine
- the molar ratio of the fatty acid to the ethanolamine substance is preferably 1:1.1-1.3, more preferably 1:1.15-1.25, and more preferably 1:1.17-1.23.
- the solid acid catalyst in step (1) comprises a carrier and an active component
- the carrier is one or more of multi-level pore HY molecular sieve, multi-level pore HZSM-5 molecular sieve, SiO 2 , TiO 2 , ⁇ -Al 2 O 3 ;
- the active component is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, germanotungstic acid, germanomolybdic acid;
- the mass ratio of the active component to the solid acid catalyst is preferably 5-25:100, more preferably 10-20:100, and more preferably 13-17:100; the mass of the solid acid catalyst is preferably 0.1-1.4 wt % of the sum of the mass of the fatty acid and the ethanolamine substances, more preferably 0.3-1.1 wt %, and more preferably 0.5-0.8 wt %.
- the specific preparation method of the solid acid catalyst in step (1) can refer to patent CN113086989A or the master's thesis "Synthesis and Characterization of Multi-Level Porous ZSM-5 and Y-Type Molecular Sieve”.
- fatty acid is first added into a reactor equipped with a stirrer and a fractionation condenser, heated to completely melt, and then a solid acid catalyst is added under stirring, and ethanolamine is slowly added dropwise.
- the heating temperature is preferably 40 to 90°C, more preferably 60 to 80°C, and more preferably 65 to 75°C;
- the stirring speed is preferably 200 to 600 r/min, and more preferably 300-500r/min, more preferably 350-400r/min;
- the dropping time is preferably 10-60min, more preferably 20-50min, more preferably 30-35min.
- the temperature of the esterification reaction in step (1) is preferably 120-160°C, more preferably 130-150°C, and more preferably 135-145°C; the time of the esterification reaction is preferably 6-12h, more preferably 7-11h, and more preferably 8-10h.
- the reflux temperature is strictly controlled during the esterification reaction; the reflux temperature is preferably 40 to 70°C, more preferably 45 to 65°C, and more preferably 50 to 60°C.
- the residual ethanolamine substances are distilled off under reduced pressure, and the solid acid catalyst is filtered and recovered while hot for reuse, and then cooled to room temperature to obtain a monoalkyl ester amine intermediate.
- the chemical formula of the esterification reaction in step (1) is:
- the organic acid in step (2) is one or more of formic acid, acetic acid, propionic acid and lactic acid;
- the solvent is one or more of water, ethanol, ethylene glycol, n-propanol, isopropanol and propylene glycol.
- the molar ratio of the monoalkyl ester amine intermediate, the organic acid and epichlorohydrin in step (2) is preferably 1.9-2.1:1.0-1.1:0.9-1.0, more preferably 1.95-2.05:1.02-1.08:0.92-0.98, more preferably 1.98-2.02:1.04-1.06:0.94-0.96;
- the mass of the solvent is preferably 39-60wt% of the sum of the mass of the monoalkyl ester amine intermediate, the organic acid, the solvent and the epichlorohydrin, more preferably 45-55wt%, more preferably 47-53wt%.
- the monoalkyl ester amine intermediate, the organic acid and the solvent are first dissolved and subjected to a neutralization reaction, and then epichlorohydrin is added to carry out a quaternization reaction to obtain the diester-based Gemini quaternary ammonium salt.
- the neutralization reaction temperature is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; the neutralization reaction time is preferably 0.2-1h, more preferably 0.3-0.9h, more preferably 0.4-0.8h.
- the temperature of the quaternization reaction in step (2) is preferably 80 to 120° C., more preferably 90 to 110° C., and more preferably 95 to 105° C.; the time of the quaternization reaction is preferably 4 to 16 h, more preferably 6 to 14 h, and more preferably 8 to 12 h.
- the diester-based Gemini quaternary ammonium salt is obtained by naturally cooling to room temperature.
- the invention also provides application of the diester-based Gemini quaternary ammonium salt in disinfection and sterilization or fabric softening.
- the specific preparation method is:
- octanoic acid Under nitrogen atmosphere, 0.5 mol of octanoic acid was added to a reactor equipped with a stirrer and a fractionation condenser, heated to 50°C to completely melt it, and 0.26 g of 8 wt% phosphotungstic acid/multi-level HY molecular sieve was added under stirring at 300 r/min, and 0.65 mol of dimethylethanolamine was slowly added dropwise. The addition took about 20 min. After the addition was completed, the temperature was raised to 120°C and the reaction was kept at a constant temperature for 6 h. The reflux temperature was strictly controlled. The temperature was 50° C. After the reaction was completed, the residual dimethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse, and then cooled to room temperature to obtain ethyl octanoate dimethyl tertiary amine.
- the specific preparation method is:
- the specific preparation method is:
- a reactor equipped with a stirrer and a fractionating condenser Under nitrogen atmosphere, 0.5 mol palmitic acid is added into a reactor equipped with a stirrer and a fractionating condenser, and heated to 80°C to completely melt it. Under stirring at 350 r/min, 1.16 g of silicomolybdic acid/multi-level pore HY molecular sieve with a loading of 12 wt% is added, and 0.65 mol dimethylethanolamine is slowly added dropwise. The addition takes about 35 minutes. After the addition is completed, the temperature is raised to 160°C and the reaction is carried out at a constant temperature for 10 hours. The reflux temperature is strictly controlled to be 50°C. After the reaction is completed, the residual dimethylethanolamine is evaporated under reduced pressure and the solid acid catalyst is recovered by hot filtration for reuse, and cooled to room temperature to obtain palmitic acid ethyl dimethyl tertiary amine.
- the specific preparation method is:
- the specific preparation method is:
- the specific preparation method is:
- the specific preparation method is:
- the specific preparation method is:
- stearic acid Under nitrogen atmosphere, 0.5 mol of stearic acid was added into a reactor equipped with a stirrer and a fractionating condenser, and heated to 88°C to completely melt it.
- 2.80 g of silicotungstic acid/multi-level pore HZSM-5 molecular sieve with a loading of 22 wt% was added under stirring at 500 r/min, and 0.60 mol of diethylethanolamine was slowly added dropwise. The addition took about 50 min. After the addition was completed, the temperature was raised to 160°C and the reaction was carried out at a constant temperature for 12 h. The reflux temperature was strictly controlled to 70°C.
- the diester-based Gemini quaternary ammonium salt products obtained in Example 2 and Example 4 were diluted with water to a solid content of 5wt%, and then subjected to acute oral toxicity test and a complete skin irritation test.
- the results of the acute oral toxicity test showed that during the test of the products obtained in Example 2 and Example 4, no obvious symptoms of poisoning and death were observed in all the test animals during the 14-day observation period, and the acute oral toxicity LD50 of the products to SPF-grade KM mice was >5000mg/kg ⁇ BW, which was actually non-toxic; the results of the complete skin irritation test showed that the products obtained in Example 2 and Example 4 were non-irritating to the complete skin test results of New Zealand rabbits.
- Example 2 and Example 4 According to the national standard GB/T15818-2006 "Test Method for Biodegradability of Surfactants", the seventh-day primary biodegradability of the products obtained in Example 2 and Example 4 was tested by the Golden Orange II method. The test results show that the seventh-day primary biodegradability of the products obtained in Example 2 and Example 4 is 99% and 97% respectively, which have excellent biodegradability and can be defined as "green surfactants".
- Example 2 The products synthesized in Example 2 and Example 5 were tested for antibacterial effect using the suspension quantitative method according to the standard QB/T2738-2012 "Evaluation method for antibacterial and antimicrobial effects of daily chemical products". The test results are shown in Table 1.
- DDAC is a traditional quaternary ammonium salt - di-C10 alkyl dimethyl ammonium chloride.
- Example 2 and Example 5 show excellent antibacterial performance (antibacterial logarithm value>5) against Staphylococcus aureus, Escherichia coli, Candida albicans and Pseudomonas aeruginosa at a mass concentration of 20ppm and 10ppm.
- the new diester-based Gemini quaternary ammonium salt has a better antibacterial effect on different strains, especially the difference in the inhibitory effect on Candida albicans is the most obvious.
- the diester-based Gemini quaternary ammonium salt synthesized by the present invention has potential market application value in the field of inhibition/bactericidal.
- Example 4 The sample synthesized in Example 4 was diluted with water to an aqueous solution with a solid content of 5 wt%, and hard water was added to prepare sample solutions with different mass concentrations (0.1 g/L, 0.2 g/L, 0.5 g/L, 1.0 g/L) for testing; according to the provisions of the reference standard QB/T4535-2013 "Fabric Softener", knitted cotton white cloth was selected as the test fabric, and the softness of the sample was tested by the DRK119R softness tester of Shandong Derui Instrument Co., Ltd., and compared with commercially available softener products. The results are shown in Table 2.
- Example 4 sample As shown in Table 2, with the increase of the mass concentration of the three softener samples, the softness of the fabric is significantly reduced, and the softness variation can reach more than 100mN.
- the three softeners are ranked as follows: D1821> Example 4 sample> ester quaternary ammonium salt.
- the softening performance of Example 4 sample is better than that of ester quaternary ammonium salt, and the special double hydrophilic head group structure of the patented product makes the product have better water solubility than ester quaternary ammonium salt, and the actual application effect is better.
- the excellent comprehensive application performance of the patented product gives it a good market prospect in the field of fabric softening and antistatic.
- the diester-based Gemini quaternary ammonium salt product provided by the present invention has no obvious poisoning symptoms or death in the acute oral toxicity test of all the test animals during the 14-day observation period, and the acute oral toxicity LD50 of the sample to SPF-level KM mice is >5000mg/kg ⁇ BW, which is actually non-toxic; in a complete skin irritation test, the sample is non-irritating to the complete skin test result of New Zealand rabbits; the primary biodegradability of the sample on the seventh day is as high as 99%, which can be defined as a "green surfactant"; it exhibits excellent antibacterial properties against Staphylococcus aureus, Escherichia coli, Candida albicans and Pseudomonas aeruginosa (antibacterial logarithm value >5); the softness is better than that of ester-based quaternary ammonium salts, and the special double hydrophilic head group structure makes the product have better water so
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Abstract
Provided are a diester-based Gemini quaternary ammonium salt as well as a preparation method therefor and a use thereof. An obtained product may be used as a primary component of a fabric softener, and may also be used as a main bactericidal component of an antibacterial detergent.
Description
本发明涉及阳离子表面活性剂技术领域，尤其涉及一种双酯基Gemini季铵盐及其制备方法和应用。The invention relates to the technical field of cationic surfactants, and in particular to a diester-based Gemini quaternary ammonium salt and a preparation method and application thereof.
织物纤维在使用一段时间后通常会出现僵硬、手感粗糙等不良现象(尤其是棉织物)，会给使用者带来诸多不便。目前常用的解决办法是对织物进行柔软处理，织物柔软剂通过静电吸引与织物纤维表面负电荷相结合，并附着于其表面，这赋予了织物更柔软蓬松的质感，并且有助于减少织物皱纹，给予织物愉悦的香味。随着人们生活品质的提升，织物柔软剂市场需求呈持续增长态势。目前织物柔软剂主成分主要是有机硅表面活性剂类和阳离子表面活性剂季铵盐类，季铵盐类主要包括：烷基三甲基铵盐、双烷基二甲基铵盐、双酰胺基烷氧基铵盐和咪唑啉铵盐等。其中，传统织物柔软剂双烷基季铵盐(以D1821为主)具有优良的织物柔软性，但存在生物降解性差、易使织物泛黄、复配性差、生产成本高、不易配制高浓缩产品等不足，尤其对环境污染较为严重，从上世纪90年代开始德国等欧洲主要发达国家就已停用该类产品。为适应市场化需求，近30年来世界各国研究者们都在争相开发兼具优良应用性能和绿色环保特性的新一代织物柔软剂产品。酯基季铵盐(主要指双长链酯基季铵盐)的出现克服了D1821存在的生物降解性差、易使织物泛黄等部分缺陷，被认为是继直链烷基苯磺酸钠(ABS)代替支链ABS后表面活性剂历史上的第二大变革。但由于酯基季铵盐合成工艺的局限性不可避免会生成部分三酯季铵盐副产物，严重影响了其水溶性和柔软性，使其综合性能难以达到D1821的水平。After a period of use, fabric fibers usually become stiff and feel rough (especially cotton fabrics), which can cause a lot of inconvenience to users. The current common solution is to soften the fabric. Fabric softeners combine with the negative charge on the surface of fabric fibers through electrostatic attraction and adhere to their surface, which gives the fabric a softer and fluffy texture, helps reduce fabric wrinkles, and gives the fabric a pleasant fragrance. With the improvement of people's quality of life, the market demand for fabric softeners continues to grow. At present, the main components of fabric softeners are mainly silicone surfactants and cationic surfactants quaternary ammonium salts. Quaternary ammonium salts mainly include: alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, diamide alkoxy ammonium salts and imidazoline ammonium salts. Among them, traditional fabric softener dialkyl quaternary ammonium salts (mainly D1821) have excellent fabric softness, but have poor biodegradability, easy to make fabric yellowing, poor compatibility, high production cost, and difficulty in preparing high-concentration products. In particular, they are more polluting to the environment. Since the 1990s, major European developed countries such as Germany have stopped using such products. In order to meet the market demand, researchers from all over the world have been competing to develop a new generation of fabric softener products with excellent application performance and green environmental protection characteristics in the past 30 years. The emergence of ester quaternary ammonium salts (mainly referring to di-long-chain ester quaternary ammonium salts) has overcome some of the defects of D1821, such as poor biodegradability and easy yellowing of fabrics. It is considered to be the second major change in the history of surfactants after linear alkylbenzene sulfonate (ABS) replaced branched ABS. However, due to the limitations of the synthesis process of ester quaternary ammonium salts, some triester quaternary ammonium salt by-products will inevitably be generated, which seriously affects its water solubility and softness, making it difficult for its comprehensive performance to reach the level of D1821.
Gemini阳离子表面活性剂的出现为新型织物柔软剂分子结构设计提供了全新思路。作为新一代即第六代季铵盐产品，Gemini季铵盐是由连接基团将两个单体季铵盐通过化学键连接而成的二聚型两亲分子，通过化学键将亲水基连接，这不仅保证了Gemini季铵盐亲水基的亲水特性，而且能够促进分子间的紧密接触。与疏水链相同的双烷基季铵盐相比，双子季铵盐具有更
好的水溶性和更低的Krafft点。Gemini季铵盐的分子特性使其具有更为优良的表/界面活性和应用性能，在杀菌消毒、织物柔软、三次采油和金属缓蚀等领域应用前景广阔。刘丹彤等以棕榈酸、二氯亚砜、N,N-二甲基乙醇胺和1,4-二溴丁烷为原料，通过酰化、酯化和季铵化反应成功合成了丁撑基双酯基Gemini季铵盐，产品在织物处理方面具有良好的再润湿性和抗黄变能力，添加少量该产品即可赋予织物柔软的手感。但由于二氯亚砜的使用，此合成方法存在工艺繁琐、环境污染严重等问题，并且二氯甲烷等毒性溶剂的使用也限制了其进一步产业化实施。牛华等以N,N-二甲基乙醇胺、硬脂酸为原料，通过酯化反应合成二甲基硬脂酸乙酯基叔胺中间体，再与十八烷基二甲基叔胺、盐酸、环氧氯丙烷通过环氧开环和季铵化反应合成了一种含酯基的Gemini季铵盐并将其应用在织物柔软领域。但合成工艺中盐酸的强腐蚀性导致对生产设备要求较高且生产作业环境较差，并且酯化反应中次磷酸等均相催化剂难以从混合体系中分离除去，会在一定程度上影响目标产品的应用性能。因此，提供一种合成工艺简易、可操作性强、产率高且无残留、绿色环保和适宜产业化实施的双酯基Gemini季铵盐成为当前亟待解决的问题。The emergence of Gemini cationic surfactants provides a new idea for the molecular structure design of new fabric softeners. As a new generation of quaternary ammonium salt products, Gemini quaternary ammonium salts are dimeric amphiphilic molecules formed by connecting two monomeric quaternary ammonium salts through chemical bonds. The hydrophilic groups are connected by chemical bonds, which not only ensures the hydrophilic properties of the hydrophilic groups of Gemini quaternary ammonium salts, but also promotes close contact between molecules. Compared with dialkyl quaternary ammonium salts with the same hydrophobic chain, Gemini quaternary ammonium salts have more Good water solubility and lower Krafft point. The molecular characteristics of Gemini quaternary ammonium salts give them better surface/interfacial activity and application performance, and they have broad application prospects in the fields of sterilization and disinfection, fabric softening, tertiary oil recovery and metal corrosion inhibition. Liu Dantong et al. used palmitic acid, thionyl chloride, N,N-dimethylethanolamine and 1,4-dibromobutane as raw materials, and successfully synthesized butylene-based diester-based Gemini quaternary ammonium salts through acylation, esterification and quaternization reactions. The product has good re-wetting and anti-yellowing ability in fabric treatment, and adding a small amount of this product can give the fabric a soft feel. However, due to the use of thionyl chloride, this synthesis method has problems such as cumbersome process and serious environmental pollution, and the use of toxic solvents such as dichloromethane also limits its further industrial implementation. Niu Hua et al. used N, N-dimethylethanolamine and stearic acid as raw materials, synthesized dimethyl stearic acid ethyl ester tertiary amine intermediates through esterification reaction, and then synthesized a Gemini quaternary ammonium salt containing ester group through epoxy ring opening and quaternization reaction with octadecyl dimethyl tertiary amine, hydrochloric acid and epichlorohydrin and applied it in the field of fabric softening. However, the strong corrosiveness of hydrochloric acid in the synthesis process leads to high requirements for production equipment and poor production working environment, and homogeneous catalysts such as hypophosphorous acid are difficult to separate and remove from the mixed system in the esterification reaction, which will affect the application performance of the target product to a certain extent. Therefore, it is an urgent problem to provide a Gemini quaternary ammonium salt with a diester group that is simple in synthesis process, strong in operability, high in yield and no residue, green and environmentally friendly, and suitable for industrial implementation.
发明内容Summary of the invention
本发明的目的在于克服现有技术中存在的问题，提供一种双酯基Gemini季铵盐及其制备方法和应用。The purpose of the present invention is to overcome the problems existing in the prior art and provide a diester-based Gemini quaternary ammonium salt and a preparation method and application thereof.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned invention object, the present invention provides the following technical solutions:
本发明提供了一种双酯基Gemini季铵盐，具有下列结构：
The present invention provides a diester-based Gemini quaternary ammonium salt having the following structure:
The present invention provides a diester-based Gemini quaternary ammonium salt having the following structure:
n为8、10、12、14、16、18或20；n is 8, 10, 12, 14, 16, 18 or 20;
R为CH3或CH2CH3；R is CH 3 or CH 2 CH 3 ;
X为HCOO、CH3COO、CH3CH2COO或CH3CH(OH)COO。
X is HCOO, CH 3 COO, CH 3 CH 2 COO or CH 3 CH(OH)COO.
本发明还提供了一种双酯基Gemini季铵盐的制备方法，包含以下步骤：The present invention also provides a method for preparing a diester-based Gemini quaternary ammonium salt, comprising the following steps:
(1)在保护氛围中，将脂肪酸、固体酸性催化剂和乙醇胺类物质混合，进行酯化反应得到单烷基酯胺中间体；(1) In a protective atmosphere, a fatty acid, a solid acid catalyst and an ethanolamine substance are mixed to carry out an esterification reaction to obtain a monoalkyl ester amine intermediate;
(2)将单烷基酯胺中间体、有机酸、溶剂和环氧氯丙烷混合，进行季铵化反应得到所述的双酯基Gemini季铵盐。(2) Mixing the monoalkyl ester amine intermediate, an organic acid, a solvent and epichlorohydrin, and performing a quaternization reaction to obtain the diester-based Gemini quaternary ammonium salt.
作为优选，步骤(1)所述脂肪酸具有以下结构：n为8、10、12、14、16、18或20；Preferably, the fatty acid in step (1) has the following structure: n is 8, 10, 12, 14, 16, 18 or 20;
所述乙醇胺类物质为二甲基乙醇胺或二乙基乙醇胺；The ethanolamine substance is dimethylethanolamine or diethylethanolamine;
所述脂肪酸和乙醇胺类物质的摩尔比为1：1.1～1.3。The molar ratio of the fatty acid to the ethanolamine substance is 1:1.1-1.3.
作为优选，步骤(1)所述固体酸性催化剂包含载体和活性组分；Preferably, the solid acid catalyst in step (1) comprises a carrier and an active component;
所述载体为多级孔HY分子筛、多级孔HZSM-5分子筛、SiO2、TiO2、γ-Al2O3中的一种或多种；所述活性组分为磷钨酸、磷钼酸、硅钨酸、硅钼酸、锗钨酸、锗钼酸中的一种或多种；The carrier is one or more of multi-level pore HY molecular sieve, multi-level pore HZSM-5 molecular sieve, SiO 2 , TiO 2 , γ-Al 2 O 3 ; the active component is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, germanotungstic acid, germanomolybdic acid;
所述活性组分与所述固体酸性催化剂的质量比为5～25：100；所述固体酸性催化剂的质量为所述脂肪酸和乙醇胺类物质的质量和的0.1～1.4wt％。The mass ratio of the active component to the solid acid catalyst is 5-25:100; the mass of the solid acid catalyst is 0.1-1.4wt% of the total mass of the fatty acid and the ethanolamine substances.
作为优选，步骤(1)所述酯化反应的温度为120～160℃，所述酯化反应的时间为6～12h。Preferably, the temperature of the esterification reaction in step (1) is 120-160° C., and the time of the esterification reaction is 6-12 hours.
作为优选，步骤(2)所述有机酸为甲酸、乙酸、丙酸和乳酸中的一种或多种；所述溶剂为水、乙醇、乙二醇、正丙醇、异丙醇和丙二醇中的一种或多种。Preferably, the organic acid in step (2) is one or more of formic acid, acetic acid, propionic acid and lactic acid; and the solvent is one or more of water, ethanol, ethylene glycol, n-propanol, isopropanol and propylene glycol.
作为优选，步骤(2)所述单烷基酯胺中间体、有机酸和环氧氯丙烷的摩尔比为1.9～2.1：1.0～1.1：0.9～1.0；所述溶剂的质量为所述单烷基酯胺中间体、有机酸、溶剂和环氧氯丙烷的质量和的39～60wt％。Preferably, in step (2), the molar ratio of the monoalkyl ester amine intermediate, the organic acid and epichlorohydrin is 1.9-2.1:1.0-1.1:0.9-1.0; and the mass of the solvent is 39-60wt% of the sum of the mass of the monoalkyl ester amine intermediate, the organic acid, the solvent and epichlorohydrin.
作为优选，步骤(2)所述季铵化反应的温度为80～120℃，所述季铵化反应的时间为4～16h。Preferably, the temperature of the quaternization reaction in step (2) is 80 to 120° C., and the time of the quaternization reaction is 4 to 16 hours.
本发明还提供了所述双酯基Gemini季铵盐在消毒杀菌或织物柔顺中的应用。The invention also provides application of the diester-based Gemini quaternary ammonium salt in disinfection and sterilization or fabric softening.
本发明的有益效果是：
The beneficial effects of the present invention are:
(1)本发明制备方法中采用非均相负载型催化剂催化酯化反应，反应效率高，催化剂稳定性好，可回收再利用，避免了传统亚磷酸等均相催化剂在产物中的残留，保证了目标产品的纯度；采用有机酸取代传统盐酸作为酸碱中和剂，避免了盐酸对生产设备的腐蚀，生产装置要求简易且作业环境相对安全。(1) In the preparation method of the present invention, a heterogeneous supported catalyst is used to catalyze the esterification reaction, which has high reaction efficiency, good catalyst stability, and can be recycled and reused, thereby avoiding the residue of traditional homogeneous catalysts such as phosphorous acid in the product and ensuring the purity of the target product; an organic acid is used instead of traditional hydrochloric acid as an acid-base neutralizer to avoid the corrosion of hydrochloric acid to the production equipment, and the production equipment requirements are simple and the working environment is relatively safe.
(2)本发明制备得到的产品为一类新型含有机酸反离子双酯基Gemini季铵盐，较低的氯离子含量使其在实际应用中对金属材质类设备基本无腐蚀性；产品水溶性良好，生物降解性好，并具备低毒低刺激的特点，在消毒杀菌、织物柔顺等领域相比传统烷基季铵盐优势明显，可用于公共场所、皮肤和黏膜的消毒；具有杀菌效率高和抗菌谱图广的特点，作为织物柔软剂的主成分来使用，在织物柔顺性上与传统D1821和酯基季铵盐相当；并且产品与阴离子、非离子表面活性剂配伍性优良，可作为抑菌性洗涤剂的主成分来使用。(2) The product prepared by the present invention is a new type of diester-based Gemini quaternary ammonium salt containing organic acid counterions. The low chloride ion content makes it basically non-corrosive to metal equipment in practical applications; the product has good water solubility, good biodegradability, and the characteristics of low toxicity and low irritation. It has obvious advantages over traditional alkyl quaternary ammonium salts in the fields of disinfection, sterilization, fabric softening, etc., and can be used for disinfection of public places, skin and mucous membranes; it has the characteristics of high bactericidal efficiency and a wide antibacterial spectrum, and is used as the main component of a fabric softener. The fabric softening is comparable to that of traditional D1821 and ester-based quaternary ammonium salts; and the product has excellent compatibility with anionic and nonionic surfactants, and can be used as the main component of an antibacterial detergent.
(3)本发明制备得到的产品，在急性经口毒性试验中，14天观察期内所有受试动物未见明显中毒症状和死亡，样品对SPF级KM小鼠急性经口毒性LD50>5000mg/kg·BW，属于实际无毒级；在一次完整皮肤刺激性试验中，样品对新西兰兔一次完整皮肤试验结果为无刺激性；样品的第七天初级生物降解度高达99％，可定义为“绿色表面活性剂”；对金黄色葡萄球菌、大肠杆菌、白色念球真菌和铜绿假单胞菌都表现出优异的抑菌性能(抑菌对数值＞5)；柔软性能优于酯基季铵盐，并且特殊的双亲水头基结构使该产品相比酯基季铵盐具备更为优良的水溶性，实际应用效果更佳。(3) In the acute oral toxicity test, the product prepared by the present invention showed no obvious poisoning symptoms or death in all the test animals during the 14-day observation period. The acute oral toxicity LD50 of the sample to SPF-grade KM mice was greater than 5000 mg/kg·BW, which is practically non-toxic. In a complete skin irritation test, the sample was non-irritating to New Zealand rabbits in a complete skin test. The primary biodegradability of the sample on the seventh day was as high as 99%, which can be defined as a "green surfactant". It showed excellent antibacterial properties against Staphylococcus aureus, Escherichia coli, Candida albicans and Pseudomonas aeruginosa (antibacterial logarithm value > 5). The softness was better than that of ester-based quaternary ammonium salts, and the special hydrophilic head group structure made the product have better water solubility than ester-based quaternary ammonium salts, and the actual application effect was better.
本发明提供了一种双酯基Gemini季铵盐，具有下列结构：
The present invention provides a diester-based Gemini quaternary ammonium salt having the following structure:
The present invention provides a diester-based Gemini quaternary ammonium salt having the following structure:
n为8、10、12、14、16、18或20；n is 8, 10, 12, 14, 16, 18 or 20;
R为CH3或CH2CH3；R is CH 3 or CH 2 CH 3 ;
X为HCOO、CH3COO、CH3CH2COO或CH3CH(OH)COO。X is HCOO, CH 3 COO, CH 3 CH 2 COO or CH 3 CH(OH)COO.
本发明还提供了一种双酯基Gemini季铵盐的制备方法，包含以下步骤：The present invention also provides a method for preparing a diester-based Gemini quaternary ammonium salt, comprising the following steps:
(1)在保护氛围中，将脂肪酸、固体酸性催化剂和乙醇胺类物质混合，进行酯化反应得到单烷基酯胺中间体；(1) In a protective atmosphere, a fatty acid, a solid acid catalyst and an ethanolamine substance are mixed to carry out an esterification reaction to obtain a monoalkyl ester amine intermediate;
(2)将单烷基酯胺中间体、有机酸、溶剂和环氧氯丙烷混合，进行季铵化反应得到所述的双酯基Gemini季铵盐。(2) Mixing the monoalkyl ester amine intermediate, an organic acid, a solvent and epichlorohydrin, and performing a quaternization reaction to obtain the diester-based Gemini quaternary ammonium salt.
在本发明中，步骤(1)所述脂肪酸具有以下结构：n为8、10、12、14、16、18或20；In the present invention, the fatty acid in step (1) has the following structure: n is 8, 10, 12, 14, 16, 18 or 20;
所述乙醇胺类物质为二甲基乙醇胺或二乙基乙醇胺；The ethanolamine substance is dimethylethanolamine or diethylethanolamine;
所述脂肪酸和乙醇胺类物质的摩尔比优选为1：1.1～1.3，进一步优选为1：1.15～1.25，更优选为1：1.17～1.23。The molar ratio of the fatty acid to the ethanolamine substance is preferably 1:1.1-1.3, more preferably 1:1.15-1.25, and more preferably 1:1.17-1.23.
在本发明中，步骤(1)所述固体酸性催化剂包含载体和活性组分；In the present invention, the solid acid catalyst in step (1) comprises a carrier and an active component;
所述载体为多级孔HY分子筛、多级孔HZSM-5分子筛、SiO2、TiO2、γ-Al2O3中的一种或多种；所述活性组分为磷钨酸、磷钼酸、硅钨酸、硅钼酸、锗钨酸、锗钼酸中的一种或多种；The carrier is one or more of multi-level pore HY molecular sieve, multi-level pore HZSM-5 molecular sieve, SiO 2 , TiO 2 , γ-Al 2 O 3 ; the active component is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, germanotungstic acid, germanomolybdic acid;
所述活性组分与所述固体酸性催化剂的质量比优选为5～25：100，进一步优选为10～20：100，更优选为13～17：100；所述固体酸性催化剂的质量优选为所述脂肪酸和乙醇胺类物质的质量和的0.1～1.4wt％，进一步优选为0.3～1.1wt％，更优选为0.5～0.8wt％。The mass ratio of the active component to the solid acid catalyst is preferably 5-25:100, more preferably 10-20:100, and more preferably 13-17:100; the mass of the solid acid catalyst is preferably 0.1-1.4 wt % of the sum of the mass of the fatty acid and the ethanolamine substances, more preferably 0.3-1.1 wt %, and more preferably 0.5-0.8 wt %.
在本发明中，步骤(1)所述固体酸性催化剂的具体制备方法可参照专利CN113086989A或硕士论文“多级孔ZSM-5和Y型分子筛的合成与表征”。In the present invention, the specific preparation method of the solid acid catalyst in step (1) can refer to patent CN113086989A or the master's thesis "Synthesis and Characterization of Multi-Level Porous ZSM-5 and Y-Type Molecular Sieve".
在本发明中，先将脂肪酸加入带有搅拌器和分馏冷凝管的反应器中，加热使其完全熔化，然后再在搅拌状态下加入固体酸性催化剂，并缓慢滴加乙醇胺类物质。In the present invention, fatty acid is first added into a reactor equipped with a stirrer and a fractionation condenser, heated to completely melt, and then a solid acid catalyst is added under stirring, and ethanolamine is slowly added dropwise.
在本发明中，所述加热的温度优选为40～90℃，进一步优选为60～80℃，更优选为65～75℃；所述搅拌的转速优选为200～600r/min，进一步优选为
300～500r/min，更优选为350～400r/min；所述滴加的时间优选为10～60min，进一步优选为20～50min，更优选为30～35min。In the present invention, the heating temperature is preferably 40 to 90°C, more preferably 60 to 80°C, and more preferably 65 to 75°C; the stirring speed is preferably 200 to 600 r/min, and more preferably 300-500r/min, more preferably 350-400r/min; the dropping time is preferably 10-60min, more preferably 20-50min, more preferably 30-35min.
在本发明中，步骤(1)所述酯化反应的温度优选为120～160℃，进一步优选为130～150℃，更优选为135～145℃；所述酯化反应的时间优选为6～12h，进一步优选为7～11h，更优选为8～10h。In the present invention, the temperature of the esterification reaction in step (1) is preferably 120-160°C, more preferably 130-150°C, and more preferably 135-145°C; the time of the esterification reaction is preferably 6-12h, more preferably 7-11h, and more preferably 8-10h.
在本发明中，酯化反应过程中严格控制回流的温度；所述回流的温度优选为40～70℃，进一步优选为45～65℃，更优选为50～60℃。In the present invention, the reflux temperature is strictly controlled during the esterification reaction; the reflux temperature is preferably 40 to 70°C, more preferably 45 to 65°C, and more preferably 50 to 60°C.
在本发明中，酯化反应结束后减压蒸除残留的乙醇胺类物质，并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得单烷基酯胺中间体。In the present invention, after the esterification reaction is completed, the residual ethanolamine substances are distilled off under reduced pressure, and the solid acid catalyst is filtered and recovered while hot for reuse, and then cooled to room temperature to obtain a monoalkyl ester amine intermediate.
在本发明中，步骤(1)所述酯化反应的化学式为：
In the present invention, the chemical formula of the esterification reaction in step (1) is:
In the present invention, the chemical formula of the esterification reaction in step (1) is:
在本发明中，步骤(2)所述有机酸为甲酸、乙酸、丙酸和乳酸中的一种或多种；所述溶剂为水、乙醇、乙二醇、正丙醇、异丙醇和丙二醇中的一种或多种。In the present invention, the organic acid in step (2) is one or more of formic acid, acetic acid, propionic acid and lactic acid; the solvent is one or more of water, ethanol, ethylene glycol, n-propanol, isopropanol and propylene glycol.
在本发明中，步骤(2)所述单烷基酯胺中间体、有机酸和环氧氯丙烷的摩尔比优选为1.9～2.1：1.0～1.1：0.9～1.0，进一步优选为1.95～2.05：1.02～1.08：0.92～0.98，更优选为1.98～2.02：1.04～1.06：0.94～0.96；所述溶剂的质量优选为所述单烷基酯胺中间体、有机酸、溶剂和环氧氯丙烷的质量和的39～60wt％，进一步优选为45～55wt％，更优选为47～53wt％。In the present invention, the molar ratio of the monoalkyl ester amine intermediate, the organic acid and epichlorohydrin in step (2) is preferably 1.9-2.1:1.0-1.1:0.9-1.0, more preferably 1.95-2.05:1.02-1.08:0.92-0.98, more preferably 1.98-2.02:1.04-1.06:0.94-0.96; the mass of the solvent is preferably 39-60wt% of the sum of the mass of the monoalkyl ester amine intermediate, the organic acid, the solvent and the epichlorohydrin, more preferably 45-55wt%, more preferably 47-53wt%.
在本发明中，先将单烷基酯胺中间体、有机酸和溶剂进行溶解，进行中和反应，再加入环氧氯丙烷，进行季铵化反应，得到所述的双酯基Gemini季铵盐。In the present invention, the monoalkyl ester amine intermediate, the organic acid and the solvent are first dissolved and subjected to a neutralization reaction, and then epichlorohydrin is added to carry out a quaternization reaction to obtain the diester-based Gemini quaternary ammonium salt.
在本发明中，所述中和反应的温度优选为20～30℃，进一步优选为22～28℃，更优选为24～26℃；所述中和反应的时间优选为0.2～1h，进一步优选为0.3～0.9h，更优选为0.4～0.8h。In the present invention, the neutralization reaction temperature is preferably 20-30°C, more preferably 22-28°C, more preferably 24-26°C; the neutralization reaction time is preferably 0.2-1h, more preferably 0.3-0.9h, more preferably 0.4-0.8h.
在本发明中，步骤(2)所述季铵化反应的温度优选为80～120℃，进一步优选为90～110℃，更优选为95～105℃；所述季铵化反应的时间优选为4～16h，进一步优选为6～14h，更优选为8～12h。
In the present invention, the temperature of the quaternization reaction in step (2) is preferably 80 to 120° C., more preferably 90 to 110° C., and more preferably 95 to 105° C.; the time of the quaternization reaction is preferably 4 to 16 h, more preferably 6 to 14 h, and more preferably 8 to 12 h.
在本发明中，季铵化反应结束后自然冷却至室温即获得所述的双酯基Gemini季铵盐。In the present invention, after the quaternization reaction is completed, the diester-based Gemini quaternary ammonium salt is obtained by naturally cooling to room temperature.
在本发明中，所述中和反应和季铵化反应的化学式依次为：
In the present invention, the chemical formulas of the neutralization reaction and the quaternization reaction are:
In the present invention, the chemical formulas of the neutralization reaction and the quaternization reaction are:
本发明还提供了所述双酯基Gemini季铵盐在消毒杀菌或织物柔顺中的应用。The invention also provides application of the diester-based Gemini quaternary ammonium salt in disinfection and sterilization or fabric softening.
下面结合实施例对本发明提供的技术方案进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
实施例1Example 1
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol辛酸加入带有搅拌器和分馏冷凝管的反应器中，加热至50℃使其完全熔化，在300r/min的搅拌状态下加入0.26g负载量为8wt％的磷钨酸/多级孔HY分子筛，并缓慢滴加0.65mol二甲基乙醇胺，滴加耗时约20min，滴加完毕后升温至120℃恒温反应6h，严格控制回流温
度为50℃，反应结束后减压蒸除残留的二甲基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得辛酸乙酯二甲基叔胺。Under nitrogen atmosphere, 0.5 mol of octanoic acid was added to a reactor equipped with a stirrer and a fractionation condenser, heated to 50°C to completely melt it, and 0.26 g of 8 wt% phosphotungstic acid/multi-level HY molecular sieve was added under stirring at 300 r/min, and 0.65 mol of dimethylethanolamine was slowly added dropwise. The addition took about 20 min. After the addition was completed, the temperature was raised to 120°C and the reaction was kept at a constant temperature for 6 h. The reflux temperature was strictly controlled. The temperature was 50° C. After the reaction was completed, the residual dimethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse, and then cooled to room temperature to obtain ethyl octanoate dimethyl tertiary amine.
将0.4mol辛酸乙酯二甲基叔胺和0.206mol甲酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入76.1g异丙醇溶剂进行溶解，在25℃下进行中和反应0.2h，然后加入0.2mol环氧氯丙烷，升温至90℃恒温反应6h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of ethyl octanoate dimethyl tertiary amine and 0.206 mol of formic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 76.1 g of isopropanol solvent is added for dissolution. A neutralization reaction is carried out at 25°C for 0.2 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 90°C and the reaction is carried out at a constant temperature for 6 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例2Example 2
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol月桂酸加入带有搅拌器和分馏冷凝管的反应器中，加热至70℃使其完全熔化，在400r/min的搅拌状态下加入0.91g负载量为15wt％的硅钨酸/多级孔HZSM-5分子筛，并缓慢滴加0.60mol二乙基乙醇胺，滴加耗时约30min，滴加完毕后升温至140℃恒温反应10h，严格控制回流温度为70℃，反应结束后减压蒸除残留的二乙基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得月桂酸乙酯二乙基叔胺。Under nitrogen atmosphere, 0.5 mol of lauric acid is added to a reactor equipped with a stirrer and a fractionating condenser, and heated to 70°C to completely melt it. Under stirring at 400 r/min, 0.91 g of 15 wt% silicotungstic acid/multi-level pore HZSM-5 molecular sieve is added, and 0.60 mol of diethylethanolamine is slowly added dropwise. The addition takes about 30 minutes. After the addition is completed, the temperature is raised to 140°C and the reaction is carried out at a constant temperature for 10 hours. The reflux temperature is strictly controlled to be 70°C. After the reaction is completed, the residual diethylethanolamine is evaporated under reduced pressure and the solid acid catalyst is recovered by hot filtration for reuse. The mixture is cooled to room temperature to obtain lauric acid ethyl diethyl tertiary amine.
将0.4mol月桂酸乙酯二乙基叔胺和0.21mol甲酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入150g水/乙醇混合溶剂进行溶解，在26℃下进行中和反应0.5h，然后加入0.2mol环氧氯丙烷，升温至100℃恒温反应10h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。
0.4 mol of lauric acid diethyl tertiary amine and 0.21 mol of formic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 150 g of a water/ethanol mixed solvent is added for dissolution. A neutralization reaction is carried out at 26° C. for 0.5 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 100° C. and the reaction is carried out at a constant temperature for 10 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例3Example 3
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol棕榈酸加入带有搅拌器和分馏冷凝管的反应器中，加热至80℃使其完全熔化，在350r/min的搅拌状态下加入1.16g负载量为12wt％的硅钼酸/多级孔HY分子筛，并缓慢滴加0.65mol二甲基乙醇胺，滴加耗时约35min，滴加完毕后升温至160℃恒温反应10h，严格控制回流温度为50℃，反应结束后减压蒸除残留的二甲基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得棕榈酸乙酯二甲基叔胺。Under nitrogen atmosphere, 0.5 mol palmitic acid is added into a reactor equipped with a stirrer and a fractionating condenser, and heated to 80°C to completely melt it. Under stirring at 350 r/min, 1.16 g of silicomolybdic acid/multi-level pore HY molecular sieve with a loading of 12 wt% is added, and 0.65 mol dimethylethanolamine is slowly added dropwise. The addition takes about 35 minutes. After the addition is completed, the temperature is raised to 160°C and the reaction is carried out at a constant temperature for 10 hours. The reflux temperature is strictly controlled to be 50°C. After the reaction is completed, the residual dimethylethanolamine is evaporated under reduced pressure and the solid acid catalyst is recovered by hot filtration for reuse, and cooled to room temperature to obtain palmitic acid ethyl dimethyl tertiary amine.
将0.4mol棕榈酸乙酯二甲基叔胺和0.21mol乙酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入180g异丙醇混合溶剂进行溶解，在24℃下进行中和反应0.6h，然后加入0.2mol环氧氯丙烷，升温至100℃恒温反应12h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of ethyl palmitate dimethyl tertiary amine and 0.21 mol of acetic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 180 g of an isopropanol mixed solvent is added for dissolution. A neutralization reaction is carried out at 24° C. for 0.6 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 100° C. and the reaction is carried out at a constant temperature for 12 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例4Example 4
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol硬脂酸加入带有搅拌器和分馏冷凝管的反应器中，加热至90℃使其完全熔化，在450r/min的搅拌状态下加入1.49g负载量为18wt％的磷钨酸/γ-Al2O3，并缓慢滴加0.60mol二甲基乙醇胺，滴加耗时约32min，滴加完毕后升温至160℃恒温反应12h，严格控制回流温度为60℃，反应结束后减压蒸除残留的二甲基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得硬脂酸乙酯二甲基叔胺。Under nitrogen atmosphere, 0.5 mol of stearic acid was added into a reactor equipped with a stirrer and a fractional condenser, and heated to 90°C to completely melt it. Under stirring at 450 r/min, 1.49 g of phosphotungstic acid/γ-Al 2 O 3 with a loading of 18 wt% was added, and 0.60 mol of dimethylethanolamine was slowly added dropwise. The addition took about 32 minutes. After the addition was completed, the temperature was raised to 160°C and the reaction was carried out at a constant temperature for 12 hours. The reflux temperature was strictly controlled to be 60°C. After the reaction was completed, the residual dimethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse. The mixture was cooled to room temperature to obtain stearic acid ethyl dimethyl tertiary amine.
将0.4mol硬脂酸乙酯二甲基叔胺和0.21mol甲酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入205.2g异丙醇溶剂进行溶解，在28℃下进行中和反应0.6h，然后加入0.2mol环氧氯丙烷，升温至110℃恒温反应12h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of ethyl stearate dimethyl tertiary amine and 0.21 mol of formic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 205.2 g of isopropanol solvent is added for dissolution. A neutralization reaction is carried out at 28° C. for 0.6 h. Then, 0.2 mol of epichlorohydrin is added, and the temperature is raised to 110° C. for constant temperature reaction for 12 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例5Example 5
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol月桂酸加入带有搅拌器和分馏冷凝管的反应器中，加热至75℃使其完全熔化，在500r/min的搅拌状态下加入0.61g负载量为10wt％的锗钨酸/多级孔HY分子筛，并缓慢滴加0.60mol二甲基乙醇胺，滴加耗时约33min，滴加完毕后升温至130℃恒温反应8h，严格控制回流温度为50℃，反应结束后减压蒸除残留的二甲基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得月桂酸乙酯二甲基叔胺。Under nitrogen atmosphere, 0.5 mol of lauric acid was added into a reactor equipped with a stirrer and a fractionating condenser, and heated to 75°C to completely melt it. 0.61 g of germanium tungstic acid/multi-level pore HY molecular sieve with a loading of 10 wt% was added under stirring at 500 r/min, and 0.60 mol of dimethylethanolamine was slowly added dropwise. The addition took about 33 minutes. After the addition was completed, the temperature was raised to 130°C and the reaction was carried out at a constant temperature for 8 hours. The reflux temperature was strictly controlled to be 50°C. After the reaction was completed, the residual dimethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse. The reaction was cooled to room temperature to obtain ethyl laurate dimethyl tertiary amine.
将0.4mol月桂酸乙酯二甲基叔胺和0.22mol丙酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入139.1g正丙醇溶剂进行溶解，在30℃下进行中和反应0.8h，然后加入0.2mol环氧氯丙烷，升温至120℃恒温反应16h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of ethyl laurate dimethyl tertiary amine and 0.22 mol of propionic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 139.1 g of n-propanol solvent is added for dissolution. A neutralization reaction is carried out at 30°C for 0.8 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 120°C and the reaction is carried out at a constant temperature for 16 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例6Example 6
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol月桂酸加入带有搅拌器和分馏冷凝管的反应器中，加热至85℃使其完全熔化，在550r/min的搅拌状态下加入1.09g负载量为25wt％的磷钼酸/SiO2，并缓慢滴加0.55mol二乙基乙醇胺，滴加耗时约40min，滴加完毕后升温至150℃恒温反应10h，严格控制回流温度为70℃，反应结束后减压蒸除残留的二乙基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得月桂酸乙酯二乙基叔胺。
Under nitrogen atmosphere, 0.5 mol of lauric acid was added into a reactor equipped with a stirrer and a fractional condenser, and heated to 85°C to completely melt it. Under stirring at 550 r/min, 1.09 g of phosphomolybdic acid/SiO 2 with a loading of 25 wt% was added, and 0.55 mol of diethylethanolamine was slowly added dropwise. The addition took about 40 min. After the addition was completed, the temperature was raised to 150°C and the reaction was carried out at a constant temperature for 10 h. The reflux temperature was strictly controlled to be 70°C. After the reaction was completed, the residual diethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse. The reaction was cooled to room temperature to obtain lauric acid ethyl diethyl tertiary amine.
将0.4mol月桂酸乙酯二乙基叔胺和0.214mol乳酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入180.4g乙二醇溶剂进行溶解，在22℃下进行中和反应0.5h，然后加入0.2mol环氧氯丙烷，升温至100℃恒温反应12h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of lauric acid ethyl diethyl tertiary amine and 0.214 mol of lactic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 180.4 g of ethylene glycol solvent is added for dissolution. A neutralization reaction is carried out at 22° C. for 0.5 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 100° C. and the reaction is carried out at a constant temperature for 12 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例7Example 7
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol棕榈酸加入带有搅拌器和分馏冷凝管的反应器中，加热至82℃使其完全熔化，在460r/min的搅拌状态下加入1.59g负载量为16wt％的锗钼酸/TiO2，并缓慢滴加0.60mol二甲基乙醇胺，滴加耗时约38min，滴加完毕后升温至150℃恒温反应12h，严格控制回流温度为50℃，反应结束后减压蒸除残留的二甲基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得棕榈酸乙酯二甲基叔胺。Under nitrogen atmosphere, 0.5 mol palmitic acid was added into a reactor equipped with a stirrer and a fractional condenser, and heated to 82°C to completely melt it. Under stirring at 460 r/min, 1.59 g of germanomolybdic acid/TiO 2 with a loading of 16 wt% was added, and 0.60 mol dimethylethanolamine was slowly added dropwise. The addition took about 38 min. After the addition was completed, the temperature was raised to 150°C for constant temperature reaction for 12 h. The reflux temperature was strictly controlled to be 50°C. After the reaction was completed, the residual dimethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse. The solid acid catalyst was cooled to room temperature to obtain palmitic acid ethyl dimethyl tertiary amine.
将0.4mol棕榈酸乙酯二甲基叔胺和0.206mol甲酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入188.1g异丙醇溶剂进行溶解，在25℃下进行中和反应0.5h，然后加入0.2mol环氧氯丙烷，升温至110℃恒温反应10h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of ethyl palmitate dimethyl tertiary amine and 0.206 mol of formic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 188.1 g of isopropanol solvent is added for dissolution. A neutralization reaction is carried out at 25° C. for 0.5 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 110° C. and the reaction is carried out at a constant temperature for 10 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
实施例8Example 8
双酯基Gemini季铵盐的化学结构式如下：
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
The chemical structure of diester-based Gemini quaternary ammonium salt is as follows:
具体制备方法为：The specific preparation method is:
在氮气氛围下，将0.5mol硬脂酸加入带有搅拌器和分馏冷凝管的反应器中，加热至88℃使其完全熔化，在500r/min的搅拌状态下加入2.80g负载量为22wt％的硅钨酸/多级孔HZSM-5分子筛，并缓慢滴加0.60mol二乙基乙醇胺，滴加耗时约50min，滴加完毕后升温至160℃恒温反应12h，严格控制回流温度为70℃，反应结束后减压蒸除残留的二乙基乙醇胺并趁热过滤回收固体酸性催化剂以重复利用，冷却至室温获得硬脂酸乙酯二乙基叔胺。Under nitrogen atmosphere, 0.5 mol of stearic acid was added into a reactor equipped with a stirrer and a fractionating condenser, and heated to 88°C to completely melt it. 2.80 g of silicotungstic acid/multi-level pore HZSM-5 molecular sieve with a loading of 22 wt% was added under stirring at 500 r/min, and 0.60 mol of diethylethanolamine was slowly added dropwise. The addition took about 50 min. After the addition was completed, the temperature was raised to 160°C and the reaction was carried out at a constant temperature for 12 h. The reflux temperature was strictly controlled to 70°C. After the reaction was completed, the residual diethylethanolamine was evaporated under reduced pressure and the solid acid catalyst was recovered by hot filtration for reuse. The mixture was cooled to room temperature to obtain stearic acid ethyl diethyl tertiary amine.
将0.4mol硬脂酸乙酯二乙基叔胺和0.21mol甲酸加入带有搅拌器和控温装置的玻璃耐压反应器中并加入223.1g乙醇溶剂进行溶解，在26℃下进行中和反应0.6h，然后加入0.2mol环氧氯丙烷，升温至120℃恒温反应14h，结束后冷却至室温，得到所述的双酯基Gemini季铵盐。0.4 mol of ethyl stearate diethyl tertiary amine and 0.21 mol of formic acid are added into a glass pressure-resistant reactor equipped with a stirrer and a temperature control device, and 223.1 g of ethanol solvent is added for dissolution. A neutralization reaction is carried out at 26°C for 0.6 h, and then 0.2 mol of epichlorohydrin is added. The temperature is raised to 120°C and the reaction is carried out at a constant temperature for 14 h. After the reaction is completed, the reaction is cooled to room temperature to obtain the diester-based Gemini quaternary ammonium salt.
将实施例2和实施例4得到的双酯基Gemini季铵盐产品加水稀释至固含量为5wt％，随后进行急性经口毒性试验和一次完整皮肤刺激试验测试。急性经口毒性试验结果表明：实施例2和实施例4得到的产品试验过程中，14天观察期内所有受试动物未见明显中毒症状和死亡，产品对SPF级KM小鼠急性经口毒性LD50>5000mg/kg·BW，属于实际无毒级；一次完整皮肤刺激性试验结果表明：实施例2和实施例4得到的产品对新西兰兔一次完整皮肤试验结果均为无刺激性。The diester-based Gemini quaternary ammonium salt products obtained in Example 2 and Example 4 were diluted with water to a solid content of 5wt%, and then subjected to acute oral toxicity test and a complete skin irritation test. The results of the acute oral toxicity test showed that during the test of the products obtained in Example 2 and Example 4, no obvious symptoms of poisoning and death were observed in all the test animals during the 14-day observation period, and the acute oral toxicity LD50 of the products to SPF-grade KM mice was >5000mg/kg·BW, which was actually non-toxic; the results of the complete skin irritation test showed that the products obtained in Example 2 and Example 4 were non-irritating to the complete skin test results of New Zealand rabbits.
依据国标GB/T15818-2006《表面活性剂生物降解度试验方法》，通过金橙Ⅱ法对实施例2和实施例4所得产品的第七天初级生物降解度进行测试，
测试结果表明：实施例2和实施例4所得产品的第七天初级生物降解度分别为99％和97％，具有优异的生物降解性能，可定义为“绿色表面活性剂”。According to the national standard GB/T15818-2006 "Test Method for Biodegradability of Surfactants", the seventh-day primary biodegradability of the products obtained in Example 2 and Example 4 was tested by the Golden Orange II method. The test results show that the seventh-day primary biodegradability of the products obtained in Example 2 and Example 4 is 99% and 97% respectively, which have excellent biodegradability and can be defined as "green surfactants".
取实施例2和实施例5合成的产品，根据标准QB/T2738-2012《日化产品抗菌抑菌效果的评价方法》，采用悬液定量法进行抑菌性效果测试，得到的测试结果如表1所示。The products synthesized in Example 2 and Example 5 were tested for antibacterial effect using the suspension quantitative method according to the standard QB/T2738-2012 "Evaluation method for antibacterial and antimicrobial effects of daily chemical products". The test results are shown in Table 1.
表1双酯基Gemini季铵盐的抑菌效果(作用时间：2min)
注：DDAC为传统季铵盐-双C10烷基二甲基氯化铵。Table 1 Antibacterial effect of diester-based Gemini quaternary ammonium salt (action time: 2 min)
Note: DDAC is a traditional quaternary ammonium salt - di-C10 alkyl dimethyl ammonium chloride.
注：DDAC为传统季铵盐-双C10烷基二甲基氯化铵。Table 1 Antibacterial effect of diester-based Gemini quaternary ammonium salt (action time: 2 min)
Note: DDAC is a traditional quaternary ammonium salt - di-C10 alkyl dimethyl ammonium chloride.
从表1中可以得到：当抑菌作用时间为2min时，实施例2和实施例5所得产品在质量浓度为20ppm和10ppm的情况下，对金黄色葡萄球菌、大肠杆菌、白色念球真菌和铜绿假单胞菌都表现出优异的抑菌性能(抑菌对数值＞5)。相比于传统季铵盐DDAC，新型双酯基Gemini季铵盐对不同菌种具有更优的抑菌效果，尤其对白色念球真菌的抑制效果差异最为明显。本发明合成的双酯基Gemini季铵盐在抑/杀菌领域具备潜在的市场应用价值。It can be seen from Table 1 that when the antibacterial action time is 2 minutes, the products obtained in Example 2 and Example 5 show excellent antibacterial performance (antibacterial logarithm value>5) against Staphylococcus aureus, Escherichia coli, Candida albicans and Pseudomonas aeruginosa at a mass concentration of 20ppm and 10ppm. Compared with the traditional quaternary ammonium salt DDAC, the new diester-based Gemini quaternary ammonium salt has a better antibacterial effect on different strains, especially the difference in the inhibitory effect on Candida albicans is the most obvious. The diester-based Gemini quaternary ammonium salt synthesized by the present invention has potential market application value in the field of inhibition/bactericidal.
取实施例4合成的样品加水稀释至固含量为5wt％的水溶液，并加硬水配制成不同质量浓度(0.1g/L、0.2g/L、0.5g/L、1.0g/L)的样品溶液后待测；参考标准QB/T4535-2013《织物柔顺剂》规定，选取针织棉白布为测试布料，通过山东德瑞克仪器有限公司DRK119R型柔软度测试仪对样品柔软性能进行测试，并与市售柔软剂产品进行比较，得到的结果如表2所示。The sample synthesized in Example 4 was diluted with water to an aqueous solution with a solid content of 5 wt%, and hard water was added to prepare sample solutions with different mass concentrations (0.1 g/L, 0.2 g/L, 0.5 g/L, 1.0 g/L) for testing; according to the provisions of the reference standard QB/T4535-2013 "Fabric Softener", knitted cotton white cloth was selected as the test fabric, and the softness of the sample was tested by the DRK119R softness tester of Shandong Derui Instrument Co., Ltd., and compared with commercially available softener products. The results are shown in Table 2.
表2织物柔软性能测试结果
注：柔软度数值越小，表明柔软性能越好。Table 2 Fabric softness test results
Note: The smaller the softness value, the better the softness performance.
注：柔软度数值越小，表明柔软性能越好。Table 2 Fabric softness test results
Note: The smaller the softness value, the better the softness performance.
由表2可知，随着三种柔顺剂样品质量浓度的提高，织物柔软度明显降低，柔软度变化幅度可达100mN以上。三种柔顺剂对织物柔软性能排序为：D1821＞实施例4样品＞酯基季铵盐，实施例4样品的柔软性能优于酯基季铵盐，并且本专利产品特殊的双亲水头基结构使该产品相比酯基季铵盐具备更为优良的水溶性，实际应用效果更佳。本专利产品优良的综合应用性能使其在织物柔软、抗静电领域具备较好的市场前景。As shown in Table 2, with the increase of the mass concentration of the three softener samples, the softness of the fabric is significantly reduced, and the softness variation can reach more than 100mN. The three softeners are ranked as follows: D1821> Example 4 sample> ester quaternary ammonium salt. The softening performance of Example 4 sample is better than that of ester quaternary ammonium salt, and the special double hydrophilic head group structure of the patented product makes the product have better water solubility than ester quaternary ammonium salt, and the actual application effect is better. The excellent comprehensive application performance of the patented product gives it a good market prospect in the field of fabric softening and antistatic.
由以上实施例可知，本发明提供的双酯基Gemini季铵盐产品，在急性经口毒性试验中，14天观察期内所有受试动物未见明显中毒症状和死亡，样品对SPF级KM小鼠急性经口毒性LD50>5000mg/kg·BW，属于实际无毒级；在一次完整皮肤刺激性试验中，样品对新西兰兔一次完整皮肤试验结果为无刺激性；样品的第七天初级生物降解度高达99％，可定义为“绿色表面活性剂”；对金黄色葡萄球菌、大肠杆菌、白色念球真菌和铜绿假单胞菌都表现出优异的抑菌性能(抑菌对数值＞5)；柔软性能优于酯基季铵盐，并且特殊的双亲水头基结构使该产品相比酯基季铵盐具备更为优良的水溶性，实际应用效果更佳。It can be seen from the above embodiments that the diester-based Gemini quaternary ammonium salt product provided by the present invention has no obvious poisoning symptoms or death in the acute oral toxicity test of all the test animals during the 14-day observation period, and the acute oral toxicity LD50 of the sample to SPF-level KM mice is >5000mg/kg·BW, which is actually non-toxic; in a complete skin irritation test, the sample is non-irritating to the complete skin test result of New Zealand rabbits; the primary biodegradability of the sample on the seventh day is as high as 99%, which can be defined as a "green surfactant"; it exhibits excellent antibacterial properties against Staphylococcus aureus, Escherichia coli, Candida albicans and Pseudomonas aeruginosa (antibacterial logarithm value >5); the softness is better than that of ester-based quaternary ammonium salts, and the special double hydrophilic head group structure makes the product have better water solubility than ester-based quaternary ammonium salts, and the actual application effect is better.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims (9)
- 一种双酯基Gemini季铵盐，其特征在于，具有下列结构：
A diester-based Gemini quaternary ammonium salt, characterized in that it has the following structure:
n为8、10、12、14、16、18或20；n is 8, 10, 12, 14, 16, 18 or 20;R为CH3或CH2CH3；R is CH 3 or CH 2 CH 3 ;X为HCOO、CH3COO、CH3CH2COO或CH3CH(OH)COO。X is HCOO, CH 3 COO, CH 3 CH 2 COO or CH 3 CH(OH)COO. - 权利要求1所述双酯基Gemini季铵盐的制备方法，其特征在于，包含以下步骤：The method for preparing the diester-based Gemini quaternary ammonium salt according to claim 1, characterized in that it comprises the following steps:(1)在保护氛围中，将脂肪酸、固体酸性催化剂和乙醇胺类物质混合，进行酯化反应得到单烷基酯胺中间体；(1) In a protective atmosphere, a fatty acid, a solid acid catalyst and an ethanolamine substance are mixed to carry out an esterification reaction to obtain a monoalkyl ester amine intermediate;(2)将单烷基酯胺中间体、有机酸、溶剂和环氧氯丙烷混合，进行季铵化反应得到所述的双酯基Gemini季铵盐。(2) Mixing the monoalkyl ester amine intermediate, an organic acid, a solvent and epichlorohydrin, and performing a quaternization reaction to obtain the diester-based Gemini quaternary ammonium salt.
- 如权利要求2所述的制备方法，其特征在于，步骤(1)所述脂肪酸具有以下结构： The preparation method according to claim 2, characterized in that the fatty acid in step (1) has the following structure:n为8、10、12、14、16、18或20；n is 8, 10, 12, 14, 16, 18 or 20;所述乙醇胺类物质为二甲基乙醇胺或二乙基乙醇胺；The ethanolamine substance is dimethylethanolamine or diethylethanolamine;所述脂肪酸和乙醇胺类物质的摩尔比为1：1.1～1.3。The molar ratio of the fatty acid to the ethanolamine substance is 1:1.1-1.3.
- 如权利要求2所述的制备方法，其特征在于，步骤(1)所述固体酸性催化剂包含载体和活性组分；The preparation method according to claim 2, characterized in that the solid acid catalyst in step (1) comprises a carrier and an active component;所述载体为多级孔HY分子筛、多级孔HZSM-5分子筛、SiO2、TiO2、γ-Al2O3中的一种或多种；所述活性组分为磷钨酸、磷钼酸、硅钨酸、硅钼酸、锗钨酸、锗钼酸中的一种或多种；The carrier is one or more of multi-level pore HY molecular sieve, multi-level pore HZSM-5 molecular sieve, SiO 2 , TiO 2 , γ-Al 2 O 3 ; the active component is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, germanotungstic acid, germanomolybdic acid;所述活性组分与所述固体酸性催化剂的质量比为5～25：100；所述固体酸性催化剂的质量为所述脂肪酸和乙醇胺类物质的质量和的0.1～1.4wt％。 The mass ratio of the active component to the solid acid catalyst is 5-25:100; the mass of the solid acid catalyst is 0.1-1.4wt% of the total mass of the fatty acid and the ethanolamine substances.
- 如权利要求2～4任意一项所述的制备方法，其特征在于，步骤(1)所述酯化反应的温度为120～160℃，所述酯化反应的时间为6～12h。The preparation method according to any one of claims 2 to 4, characterized in that the temperature of the esterification reaction in step (1) is 120 to 160° C., and the time of the esterification reaction is 6 to 12 hours.
- 如权利要求5所述的制备方法，其特征在于，步骤(2)所述有机酸为甲酸、乙酸、丙酸和乳酸中的一种或多种；所述溶剂为水、乙醇、乙二醇、正丙醇、异丙醇和丙二醇中的一种或多种。The preparation method according to claim 5, characterized in that the organic acid in step (2) is one or more of formic acid, acetic acid, propionic acid and lactic acid; and the solvent is one or more of water, ethanol, ethylene glycol, n-propanol, isopropanol and propylene glycol.
- 如权利要求6所述的制备方法，其特征在于，步骤(2)所述单烷基酯胺中间体、有机酸和环氧氯丙烷的摩尔比为1.9～2.1：1.0～1.1：0.9～1.0；所述溶剂的质量为所述单烷基酯胺中间体、有机酸、溶剂和环氧氯丙烷的质量和的39～60wt％。The preparation method according to claim 6, characterized in that the molar ratio of the monoalkyl ester amine intermediate, the organic acid and epichlorohydrin in step (2) is 1.9-2.1:1.0-1.1:0.9-1.0; the mass of the solvent is 39-60wt% of the sum of the mass of the monoalkyl ester amine intermediate, the organic acid, the solvent and the epichlorohydrin.
- 如权利要求2或7所述的制备方法，其特征在于，步骤(2)所述季铵化反应的温度为80～120℃，所述季铵化反应的时间为4～16h。The preparation method according to claim 2 or 7, characterized in that the temperature of the quaternization reaction in step (2) is 80 to 120° C., and the time of the quaternization reaction is 4 to 16 hours.
- 权利要求1所述双酯基Gemini季铵盐在消毒杀菌或织物柔顺中的应用。 Use of the diester-based Gemini quaternary ammonium salt described in claim 1 in disinfection or fabric softening.
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| CN103553947A (en) * | 2013-11-05 | 2014-02-05 | 中国日用化学工业研究院 | Preparation method of hydroxyethyl-containing diester-base quaternary ammonium salt |
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| CN105503631A (en) * | 2015-12-25 | 2016-04-20 | 四川大学 | Degradable gemini quaternary ammonium salt bactericide and preparation method thereof |
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| CN114957539A (en) * | 2022-04-19 | 2022-08-30 | 万华化学集团股份有限公司 | Method for preparing porous antibacterial material from quaternary ammonium salt type GEMINI emulsifier, porous antibacterial material and application |
| CN115724754A (en) * | 2022-10-24 | 2023-03-03 | 中国日用化学研究院有限公司 | Diester Gemini quaternary ammonium salt and preparation method and application thereof |
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| CN103553946A (en) * | 2013-10-14 | 2014-02-05 | 中国日用化学工业研究院 | Synthetic method of ester tertiary amine by solid acid catalysis on aliphatic acid and ethanol amine |
| CN103553947A (en) * | 2013-11-05 | 2014-02-05 | 中国日用化学工业研究院 | Preparation method of hydroxyethyl-containing diester-base quaternary ammonium salt |
| CN105503631A (en) * | 2015-12-25 | 2016-04-20 | 四川大学 | Degradable gemini quaternary ammonium salt bactericide and preparation method thereof |
| CN112535996A (en) * | 2020-12-24 | 2021-03-23 | 广州天赐高新材料股份有限公司 | Gemini quaternary ammonium salt-containing surfactant composition |
| CN112970752A (en) * | 2021-03-01 | 2021-06-18 | 中国日用化学研究院有限公司 | Environment-friendly efficient surface disinfectant and preparation method thereof |
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| CN115724754A (en) * | 2022-10-24 | 2023-03-03 | 中国日用化学研究院有限公司 | Diester Gemini quaternary ammonium salt and preparation method and application thereof |
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