CN111286423A - Multi-effect normal-temperature neutral liquid detergent and preparation method thereof - Google Patents
Multi-effect normal-temperature neutral liquid detergent and preparation method thereof Download PDFInfo
- Publication number
- CN111286423A CN111286423A CN202010208999.4A CN202010208999A CN111286423A CN 111286423 A CN111286423 A CN 111286423A CN 202010208999 A CN202010208999 A CN 202010208999A CN 111286423 A CN111286423 A CN 111286423A
- Authority
- CN
- China
- Prior art keywords
- essential oil
- gemini surfactant
- novel anionic
- nonionic gemini
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 53
- 230000007935 neutral effect Effects 0.000 title claims abstract description 31
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004094 surface-active agent Substances 0.000 claims abstract description 63
- 239000000341 volatile oil Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001509 sodium citrate Substances 0.000 claims abstract description 27
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 16
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 74
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 61
- 239000011780 sodium chloride Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 30
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- -1 bromo-lauryl Chemical group 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 15
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 14
- 150000001555 benzenes Chemical class 0.000 claims description 14
- 229940073608 benzyl chloride Drugs 0.000 claims description 14
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- 150000005524 benzylchlorides Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 241000220317 Rosa Species 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 4
- 235000006679 Mentha X verticillata Nutrition 0.000 claims description 4
- 235000002899 Mentha suaveolens Nutrition 0.000 claims description 4
- 235000001636 Mentha x rotundifolia Nutrition 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 244000178231 Rosmarinus officinalis Species 0.000 claims description 4
- 244000223014 Syzygium aromaticum Species 0.000 claims description 4
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims description 4
- 240000002657 Thymus vulgaris Species 0.000 claims description 4
- 235000007303 Thymus vulgaris Nutrition 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000001585 thymus vulgaris Substances 0.000 claims description 4
- 244000223760 Cinnamomum zeylanicum Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims description 2
- 244000178870 Lavandula angustifolia Species 0.000 claims description 2
- 235000010663 Lavandula angustifolia Nutrition 0.000 claims description 2
- 244000179970 Monarda didyma Species 0.000 claims description 2
- 235000010672 Monarda didyma Nutrition 0.000 claims description 2
- 235000017803 cinnamon Nutrition 0.000 claims description 2
- 239000001102 lavandula vera Substances 0.000 claims description 2
- 235000018219 lavender Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 239000004753 textile Substances 0.000 abstract description 11
- 230000002265 prevention Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- 239000006081 fluorescent whitening agent Substances 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 9
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 8
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000007794 irritation Effects 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000003385 bacteriostatic effect Effects 0.000 description 4
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 241000228245 Aspergillus niger Species 0.000 description 2
- 241001515917 Chaetomium globosum Species 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241001136494 Talaromyces funiculosus Species 0.000 description 2
- 241000223261 Trichoderma viride Species 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000001516 effect on protein Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The invention provides a multi-effect normal-temperature neutral liquid detergent which is prepared from the following raw materials: novel anionic-nonionic Gemini surfactant, lauric monoglyceride, EDTA disodium, 5 wt% hydrogen peroxide, plant essential oil, sodium citrate and sodium chlorideAnd deionized water; the novel anionic-nonionic Gemini surfactant has a structural formula shown in formula I, wherein R1=CH3(CH2)11(OC2H4)23OH, and m is an integer of 5-18. The invention selects the surfactant which is easy to biodegrade as all the components, is safe and environment-friendly, achieves and exceeds the epidemic prevention standard of public textile washing in the public textile washing, improves the comprehensive benefit by more than 25 percent, saves energy, reduces consumption and has obvious environment-friendly effect.
Description
Technical Field
The invention relates to the technical field of detergents, in particular to a multi-effect normal-temperature neutral liquid detergent and a preparation method thereof.
Background
The main component of the detergent is surfactant, which is an organic compound containing two parts of hydrophilic group and lipophilic group in the molecular structure, and is generally divided into two categories of ionic surfactant and nonionic surfactant according to whether the surfactant can be decomposed into ions in an aqueous solution. The current commercial detergents generally contain fluorescent whitening agents, and after washing, the fabrics feel rough and stiff, are not suitable for bedding and public textiles (linen), and have certain irritation to the skin. Meanwhile, a large amount of heat energy and water and electricity resources are consumed by high-temperature strong alkali washing, and the environment is damaged. Therefore, there has been a trend to develop a detergent which is highly effective, low in consumption, and environmentally friendly.
The nonionic surfactant has good performances of solubilization, washing, antistatic property, small irritation, calcium soap dispersion and the like; the actual applicable pH range is wider than that of the common ionic surfactant; the anionic surfactant has good solubility, detergency and foaming performance. The invention is a novel neutral liquid detergent which integrates the latest resources and scientific concepts in the field of current daily chemical detergents, is easy to disperse and dissolve, has small using amount, does not need heating, is convenient to operate and can finish decontamination, sterilization, bacteriostasis, mildew prevention and softening at one time.
Disclosure of Invention
The invention aims to provide a multi-effect normal-temperature neutral liquid detergent and a preparation method thereof, which have good anti-aging effect.
The technical scheme of the invention is realized as follows:
the invention provides a multi-effect normal-temperature neutral liquid detergent which is prepared from the following raw materials: the novel anionic-nonionic Gemini surfactant comprises a novel anionic-nonionic Gemini surfactant, lauric monoglyceride, EDTA disodium, 5 wt% of hydrogen peroxide, plant essential oil, sodium citrate, sodium chloride and deionized water;
the novel anionic-nonionic Gemini surfactant has a structural formula shown in a formula I:
wherein R is1=CH3(CH2)11(OC2H4)23OH, and m is an integer of 5-18.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in percentage by weight: 10-15% of novel anionic-nonionic Gemini surfactant, 3-7% of lauric acid monoglyceride, 1-3% of EDTA disodium, 1-3% of 5 wt% of hydrogen peroxide, 0.01-0.1% of vegetable essential oil, 5-12% of sodium citrate, 0.15-0.5% of sodium chloride and the balance of deionized water.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in percentage by weight: 10-15% of novel anionic-nonionic Gemini surfactant, 3-7% of lauric acid monoglyceride, 1-3% of EDTA disodium, 1-3% of 5 wt% of hydrogen peroxide, 0.01-0.1% of vegetable essential oil, 5-12% of sodium citrate, 0.15-0.5% of sodium chloride and the balance of deionized water.
As a further improvement of the invention, the novel anionic-nonionic Gemini surfactant is prepared by the following method:
s1, synthesis of bromo-lauryl alcohol polyoxyethylene ether: adding excessive phosphorus tribromide into lauryl alcohol polyoxyethylene ether, standing for layering after reaction, and washing the upper layer until no pungent smell exists, wherein the upper layer is bromo-lauryl alcohol polyoxyethylene ether;
s2, synthesis of substituted benzene: adding anhydrous aluminum chloride into benzene, heating, adding bromo-lauryl alcohol polyoxyethylene ether, carrying out reduced pressure distillation after reaction to remove excessive benzene, and filtering to obtain substituted benzene;
s3, synthesis of substituted benzyl chloride: mixing paraformaldehyde, anhydrous zinc oxide and substituted benzene, introducing excessive hydrogen chloride gas, quenching reaction after the reaction, washing, drying, distilling under reduced pressure, and collecting the fraction at the temperature of 212-217 ℃ to obtain substituted benzyl chloride;
s4, synthesis of substituted benzyl polyoxyethylene ether alcohol: poly ethylene glycol with the structural formula of HO (C)2H4O)mH and m are integers of 5 to 18, the mixture is added into a reactor, metal sodium is slowly added, the mixture is slightly heated until the metal sodium is completely dissolved,adding substituted benzyl chloride, heating for reaction, and separating by column chromatography to obtain substituted benzyl polyoxyethylene ether alcohol;
s5, synthesizing a target product: after substituted benzyl polyoxyethylene ether alcohol reacts with chlorosulfonic acid, NaOH solution is added to adjust the pH value to be alkaline, and the solvent and water in the reaction system are removed under reduced pressure to obtain a target product, wherein the structure of the target product is shown as a formula I;
the above reaction sequence may be exchanged if it does not affect the results.
As a further improvement of the invention, the ratio of the amounts of the polyoxyethylene lauryl ether and the phosphorus tribromide in step S1 is 1 (3-5); in the step S2, the mass ratio of the anhydrous aluminum chloride to the benzene to the brominated polyoxyethylene lauryl ether is (0.1-0.3): (10-15): 1; in the step S3, the mass ratio of the paraformaldehyde to the anhydrous zinc oxide to the substituted benzene is (5-10): (0.2-0.4): 1; the mass ratio of the polyethylene glycol, the metallic sodium and the substituted benzyl chloride in the step S4 is (1.1-1.3): (0.1-0.2): 1; the mass ratio of the substituted benzyl polyoxyethylene ether alcohol to chlorosulfonic acid in the step S5 is 1: (1.2-1.5), wherein the NaOH solution is a 10-15 wt% NaOH solution.
As a further improvement of the invention, the plant essential oil is selected from one of lavender essential oil, rose essential oil, rosemary essential oil, lemon essential oil, bergamot essential oil, clove essential oil, mint essential oil, cinnamon essential oil and thyme essential oil.
The invention further protects a novel anionic-nonionic Gemini surfactant with a structure shown as a formula I:
wherein R is1=CH3(CH2)11(OC2H4)23OH, m is an integer of 5 to 18
The invention further protects the application of the novel anionic-nonionic Gemini surfactant in a detergent.
The invention further provides a preparation method of the multi-effect normal-temperature neutral liquid detergent, which comprises the following steps: heating deionized water to 30-40 ℃, slowly adding EDTA disodium and sodium chloride, and stirring until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 25-30 ℃, sequentially adding vegetable essential oil and 5 wt% of hydrogen peroxide, respectively stirring uniformly, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, and respectively stirring until the novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride are completely dissolved; adding sodium citrate to adjust pH to neutral.
As a further improvement of the invention, the stirring rotating speed is 300-1000 r/min.
The invention has the following beneficial effects: the novel anionic-nonionic Gemini surfactant synthesized by the invention is a novel surfactant integrating anionic, nonionic and Gemini surfactants, so that the novel anionic-nonionic Gemini surfactant has the advantages of the anionic and nonionic surfactants, is used at normal temperature, has strong detergency, good solubility, antistatic property, small irritation and the like, and has an unexpected technical effect of softness and the beneficial effect of 1+1> 2.
The lauric acid monoglyceride is a nonionic surfactant, has good antibacterial, bactericidal, mildew-proof and emulsifying properties, is a natural preservative, is commonly used as a food mildew preventive, has the advantages of low cost, good bactericidal and preservative effects, safety, no irritation and the like, is applied to a linen detergent, has a synergistic effect with a novel anionic-nonionic Gemini type surfactant, can have an equivalent or even stronger washing effect under the condition of small dosage of the detergent when used at normal temperature, and reduces the cost of the detergent.
The 5 wt% of hydrogen peroxide added in the invention has bleaching and whitening effects, so that the linen is better white and beautiful, and the addition amount is lower, thus no irritation is caused;
the invention selects the surfactant which is easy to biodegrade for all components, is safe and environment-friendly, reaches and exceeds the sanitation and epidemic prevention standard of public textile washing in the public textile (linen) washing, has no phosphorus, toxicity or skin irritation compared with the traditional detergent, is simple and convenient to operate, is beneficial to the labor protection of workers, saves heat energy, saves electric power and water consumption, shortens the working time, improves the production efficiency, protects the quality of textile fibers, prolongs the service time of textiles, prolongs the service life of washing equipment, improves the comprehensive benefit by more than 25 percent, saves energy, reduces consumption and has obvious environment-friendly effect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 Synthesis of a novel anionic-nonionic Gemini surfactant
The synthesis process route is as follows:
the preparation method comprises the following steps:
s1, synthesis of bromo-lauryl alcohol polyoxyethylene ether: adding 3mol of phosphorus tribromide into 1mol of lauryl alcohol polyoxyethylene ether (compound A), reacting at 50 ℃ for 5h, cooling, standing for layering, discarding the lower layer, and washing the upper layer with petroleum ether until no pungent smell exists, wherein the upper layer is bromo-lauryl alcohol polyoxyethylene ether (compound B);
s2, synthesis of substituted benzene: adding 1g of anhydrous aluminum chloride into 100g of benzene, heating to 30 ℃, dropwise adding 10g of bromo-lauryl alcohol polyoxyethylene ether (compound B), continuously performing reflux reaction for 1h after dropwise adding is finished for 1h, removing excessive benzene by reduced pressure distillation after the reaction, and filtering to obtain substituted benzene (compound C);
s3, synthesis of substituted benzyl chloride: mixing 50g of paraformaldehyde, 2g of anhydrous zinc oxide and 10g of substituted benzene (compound C), adding 200mL of glacial acetic acid as a solvent, stirring at 70 ℃ for reaction for 1h, introducing excessive dry hydrogen chloride gas, cooling after the reaction, quenching the reaction, extracting the organic phase for 3 times by using petroleum ether, combining the organic phases, repeatedly washing by using anhydrous sodium carbonate and deionized water until the aqueous solution is neutral, adding anhydrous sodium sulfate for drying, filtering, distilling under reduced pressure, and collecting 212-217 ℃ fraction to obtain substituted benzyl chloride (compound D);
s4, synthesis of substituted benzyl polyoxyethylene ether alcohol: 1.1mol of polyglycidyl alcohol with the structural formula of HO (C)2H4O)17C2H4OH, adding the mixture into a reactor, slowly adding 0.1mol of metal sodium, slightly heating until the metal sodium is completely dissolved, dropwise adding 1mol of substituted benzyl chloride (compound D), heating to 120 ℃ for reaction for 3 hours, cooling, extracting the organic phase for 3 times by using petroleum ether, combining the organic phases, washing the organic phases by using hydrochloric acid and deionized water in reverse until the aqueous solution is neutral, adding anhydrous sodium sulfate for drying, filtering, removing the solvent by reducing pressure, separating by column chromatography, eluting by using petroleum ether and ethyl acetate with different proportions as an eluent and using mesoporous silica gel as a chromatographic column to obtain substituted benzyl polyoxyethylene ether alcohol (compound E);
s5, synthesizing a target product: dissolving 1mol of substituted benzyl polyoxyethylene ether alcohol (compound E) in 150mL of dichloromethane, dropwise adding 1.2mol of chlorosulfonic acid, controlling the reaction temperature at 25 ℃ for reaction for 1h, adding 10 wt% of NaOH solution to adjust the pH value to 7.5, and removing dichloromethane and water in the reaction system under reduced pressure to obtain a target product (compound F), wherein the structure is shown in formula I, and the total yield is 89%.
Separating and purifying the prepared novel anionic-nonionic Gemini surfactant, tabletting with KBr to prepare a sample, and carrying out FTIR detection, wherein the result is as follows: 2952cm-12842cm as asymmetric absorption peak of stretching vibration of methylene-1Is a methylene symmetric stretching vibration absorption peak of 1577cm-1And 1472cm-11312cm as the absorption peak of the skeleton vibration of the benzene ring-1Is SO of a sulfonic acid group2Expansion absorption peak, 1270--1A stretching vibration peak of-C-O-, 1062cm-1Is an S ═ O asymmetric and symmetric telescopic vibration absorption peak of sulfonic acid group, 1041cm-1Is Ar-O-C stretching vibration absorption peak, 965cm-1、920cm-1And 864cm-1Is an isolated hydrogen out-of-plane bending vibration absorption peak on a benzene ring.
Example 2 Synthesis of novel anionic-nonionic Gemini surfactants
The preparation method comprises the following steps:
s1, synthesis of bromo-lauryl alcohol polyoxyethylene ether: adding 5mol of phosphorus tribromide into 1mol of lauryl alcohol polyoxyethylene ether (compound A), reacting for 5h at 60 ℃, cooling, standing for layering, discarding the lower layer, and washing the upper layer with petroleum ether until no pungent smell exists, wherein the upper layer is bromo-lauryl alcohol polyoxyethylene ether (compound B);
s2, synthesis of substituted benzene: adding 3g of anhydrous aluminum chloride into 150g of benzene, heating to 40 ℃, dropwise adding 10g of bromo-lauryl alcohol polyoxyethylene ether (compound B), continuously performing reflux reaction for 1h after dropwise adding is finished, removing excessive benzene by reduced pressure distillation after the reaction, and filtering to obtain substituted benzene (compound C);
s3, synthesis of substituted benzyl chloride: mixing 100g of paraformaldehyde, 4g of anhydrous zinc oxide and 10g of substituted benzene (compound C), adding 200mL of glacial acetic acid as a solvent, stirring at 80 ℃ for reaction for 1h, introducing excessive dry hydrogen chloride gas, cooling after the reaction, quenching the reaction, extracting the organic phase for 3 times by using petroleum ether, combining the organic phases, repeatedly washing by using anhydrous sodium carbonate and deionized water until the aqueous solution is neutral, adding anhydrous sodium sulfate for drying, filtering, distilling under reduced pressure, and collecting 212-217 ℃ fraction to obtain substituted benzyl chloride (compound D);
s4, synthesis of substituted benzyl polyoxyethylene ether alcohol: 1.3mol of polyglycidyl alcohol with the structural formula of HO (C)2H4O)4C2H4OH, adding the mixture into a reactor, slowly adding 0.2mol of metal sodium, slightly heating until the metal sodium is completely dissolved, dropwise adding 1mol of substituted benzyl chloride (compound D), heating to 130 ℃ for reaction for 5 hours, cooling, extracting the organic phase for 3 times by using petroleum ether, combining the organic phases, washing the organic phases by using hydrochloric acid and deionized water in reverse until the aqueous solution is neutral, adding anhydrous sodium sulfate for drying, filtering, removing the solvent by reducing pressure, separating by column chromatography, eluting by using petroleum ether and ethyl acetate with different proportions as an eluent and using mesoporous silica gel as a chromatographic column to obtain substituted benzyl polyoxyethylene ether alcohol (compound E);
s5, synthesizing a target product: dissolving 1mol of substituted benzyl polyoxyethylene ether alcohol (compound E) in 150mL of dichloromethane, dropwise adding 1.5mol of chlorosulfonic acid, controlling the reaction temperature at 30 ℃ for reaction for 2h, adding 15 wt% of NaOH solution to adjust the pH value to 8, and removing dichloromethane and water in the reaction system under reduced pressure to obtain a target product (compound F), wherein the structure is shown in a formula I, and the total yield is 94%.
Example 3
The raw materials comprise (by weight percent): 10% of the novel anionic-nonionic Gemini surfactant prepared in example 1, 3% of lauric monoglyceride, 1% of disodium EDTA, 1% of 5 wt% of hydrogen peroxide, 0.01% of clove essential oil, 5% of sodium citrate, 0.15% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 30 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 300r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 25 ℃, sequentially adding clove essential oil and 5 wt% of hydrogen peroxide, respectively stirring uniformly at 1000r/min, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, and respectively stirring at 300r/min until the mixture is completely dissolved; adding sodium citrate to adjust pH to neutral.
Example 4
The raw materials comprise (by weight percent): 15% of the novel anionic-nonionic Gemini surfactant prepared in example 1, 7% of lauric monoglyceride, 3% of disodium EDTA, 3% of 5 wt% of hydrogen peroxide, 0.1% of thyme essential oil, 12% of sodium citrate, 0.5% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 40 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 1000r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 30 ℃, sequentially adding thyme essential oil and 5 wt% of hydrogen peroxide, respectively stirring uniformly at 1000r/min, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, and respectively stirring at 1000r/min until the mixture is completely dissolved; adding sodium citrate to adjust pH to neutral.
Example 5
The raw materials comprise (by weight percent): 12% of the novel anionic-nonionic Gemini surfactant prepared in example 2, 4% of lauric monoglyceride, 2% of disodium EDTA, 1.5% of 5 wt% hydrogen peroxide, 0.05% of mint essential oil, 7% of sodium citrate, 0.25% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 32 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 500r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 27 ℃, sequentially adding mint essential oil and 5 wt% of hydrogen peroxide, respectively stirring uniformly at 1000r/min, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, respectively stirring at 500r/min until the components are completely dissolved; adding sodium citrate to adjust pH to neutral.
Example 6
The raw materials comprise (by weight percent): 14% of the novel anionic-nonionic Gemini surfactant prepared in example 2, 6% of lauric monoglyceride, 3% of disodium EDTA, 2.5% of 5 wt% hydrogen peroxide, 0.09% of rosemary essential oil, 10% of sodium citrate, 0.45% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 38 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 800r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 29 ℃, sequentially adding rosemary essential oil and 5 wt% hydrogen peroxide, respectively stirring uniformly at 800r/min, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, and respectively stirring at 800r/min until complete dissolution; adding sodium citrate to adjust pH to neutral.
Example 7
The raw materials comprise (by weight percent): 13% of the novel anionic-nonionic Gemini surfactant prepared in example 2, 5% of lauric monoglyceride, 2.5% of disodium EDTA, 2% of 5 wt% of hydrogen peroxide, 0.07% of rose essential oil, 8% of sodium citrate, 0.35% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 35 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 600r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 27 ℃, sequentially adding rose essential oil and 5 wt% of hydrogen peroxide, respectively stirring uniformly at 1000r/min, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, respectively stirring at 600r/min until the mixture is completely dissolved; adding sodium citrate to adjust pH to neutral.
Comparative example 1
Compared with example 7, the novel anionic-nonionic Gemini surfactant prepared in example 2 is not added, and other conditions are not changed.
The raw materials comprise (by weight percent): 18% of lauric acid monoglyceride, 2.5% of EDTA disodium, 2% of 5 wt% of hydrogen peroxide, 0.07% of rose essential oil, 8% of sodium citrate, 0.35% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 35 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 600r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 27 deg.C, sequentially adding oleum Rosae Rugosae and 5 wt% hydrogen peroxide, respectively stirring at 1000r/min, cooling to room temperature, adding lauric monoglyceride, and respectively stirring at 600r/min until completely dissolved; adding sodium citrate to adjust pH to neutral.
Comparative example 2
No lauric monoglyceride was added, and other conditions were unchanged from example 7.
The raw materials comprise (by weight percent): 18% of the novel anionic-nonionic Gemini surfactant prepared in example 2, 2.5% of disodium EDTA, 2% of 5 wt% hydrogen peroxide, 0.07% of rose essential oil, 8% of sodium citrate, 0.35% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 35 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 600r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 27 ℃, sequentially adding rose essential oil and 5 wt% hydrogen peroxide, respectively stirring uniformly at 1000r/min, cooling to room temperature, adding a novel anionic-nonionic Gemini surfactant, and respectively stirring at 600r/min until completely dissolving; adding sodium citrate to adjust pH to neutral.
Comparative example 3
Compared with example 7, lauric acid monoglyceride was replaced by butyl p-hydroxybenzoate, and other conditions were not changed.
The raw materials comprise (by weight percent): 13% of the novel anionic-nonionic Gemini surfactant prepared in example 2, 5% of butyl p-hydroxybenzoate, 2.5% of disodium EDTA, 2% of 5 wt% of hydrogen peroxide, 0.07% of rose essential oil, 8% of sodium citrate, 0.35% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 35 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 600r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 27 ℃, sequentially adding rose essential oil and 5 wt% hydrogen peroxide, respectively stirring uniformly at 1000r/min, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and butyl p-hydroxybenzoate, and respectively stirring at 600r/min until the compounds are completely dissolved; adding sodium citrate to adjust pH to neutral.
Comparative example 4
Compared with the embodiment 7, 5 wt% of hydrogen peroxide is replaced by the fluorescent whitening agent JD-3, and other conditions are not changed.
The raw materials comprise (by weight percent): 13% of the novel anionic-nonionic Gemini surfactant prepared in example 2, 5% of lauric monoglyceride, 2.5% of disodium EDTA, a fluorescent whitening agent JD-32%, 0.07% of rose essential oil, 8% of sodium citrate, 0.35% of sodium chloride and the balance of deionized water.
The preparation method comprises the following steps: the method comprises the following steps: heating deionized water to 35 ℃, slowly adding EDTA disodium and sodium chloride, and stirring at 600r/min until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 27 ℃, sequentially adding rose essential oil and a fluorescent whitening agent JD-3, uniformly stirring at 1000r/min respectively, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, and stirring at 600r/min respectively until the mixture is completely dissolved; adding sodium citrate to adjust pH to neutral.
Test example 1 Performance test
The detergents prepared in examples 3 to 7 and comparative examples 1 to 4 were tested according to the relevant test items in QB/T1224-2012, and the test results are shown in the following Table 1:
TABLE 1
Note that: the pH value detection result is 7.0-7.2, which can be considered as neutral, has no stimulation to human body and no damage to clothes; in the detergency project, three national standard dirty cloths [ namely carbon black dirty cloth (JB-01), protein dirty cloth (JB-02) and sebum dirty cloth (JB-03) ] in the national standard for evaluating the detergency performance of the detergent are adopted to measure the detergency of the detergent, and the test concentration is as follows: 0.2% of standard laundry detergent and 0.2% of detergent sample.
As can be seen from the data, the detergents prepared according to examples 3-7 all have better detergency than standard laundry detergents, and especially have good removal effect on protein stains. All other performances are better than the detergents prepared in comparative examples 1-4.
Comparative example 1 and comparative example 2 compared with example 7, the novel anionic Gemini surfactant or lauric monoglyceride prepared in example 2, respectively, was not added, and the detergency was significantly inferior to that of example 7, and it was found that the novel anionic Gemini surfactant and lauric monoglyceride prepared in example 2 had a synergistic effect;
compared with the example 7, the lauric acid monoglyceride is replaced by the butyl p-hydroxybenzoate, and the performances of the comparative example 3 are basically similar to those of the example 7 and meet the national standard requirements.
Compared with the embodiment 7, the 5 wt% of hydrogen peroxide is replaced by the fluorescent whitening agent JD-3, the total content of P2O5 is 1.2%, the standard requirement is exceeded, and the fluorescent whitening agent JD-3 contains a large amount of phosphorus.
Test example 2 softness test
The softness of the fabrics after washing was tested according to the AATCC hand Test standard (AATCC Test Method 202-2012) for the detergents made in examples 3-7 and comparative examples 1-4, as well as for the commercial detergents (blue moon company). As shown in table 2 below.
TABLE 2
As can be seen from the data, the detergents prepared according to examples 3 to 7 have better softness of the washed fabrics and are obviously better than the commercial detergents and the detergents prepared according to comparative examples 1 to 4.
In comparison with example 7, in comparative examples 1 and 2, the novel anionic Gemini surfactant or monolaurate prepared in example 2 was not added, and it was found that the addition of the novel anionic Gemini surfactant and the monolaurate had a synergistic effect.
Comparative example 3 is not much different in flexibility from example 7.
Compared with the example 7, in the comparative example 4, 5 wt% of hydrogen peroxide is replaced by the fluorescent whitening agent JD-3, the softness is slightly reduced, and therefore, the addition of the fluorescent whitening agent JD-3 has a certain negative effect on the softness of the detergent.
Test example 3 mildew-proof and bacteriostatic test
1. And (3) degerming experiment: according to the sterilization rate test method in the sanitation Specification for disposable sanitary articles, the test concentration of the test method is 1% of the laundry detergent, the test method acts for 2 minutes, 5 minutes and 10 minutes at the temperature of 20-21 ℃, and the test strains are 2 strains of Staphylococcus aureus (Staphylococcus aureus, ATCC6538) and escherichia coli (Escherichia coli, 8099).
2. And (3) mildew prevention experiment: according to the test method experiment of fabric mildew resistance evaluation, the test concentration is 1% of the laundry detergent, the laundry detergent acts for 2 minutes, 5 minutes and 10 minutes, and the test strains are four kinds of moulds, namely Aspergillus niger (Aspergillus, ATCC16404), Trichoderma viride (AS 3.2941), Penicillium funiculosum (GIM 3.103) and Chaetomium globosum (AS 3.3601).
Experiments were carried out using examples 3-7 and comparative examples 1-4, the blank control containing no detergent as described above.
The results of the experiments are shown in tables 3 and 4 below.
TABLE 3 Sterilization results
TABLE 4 results of the mildew-proofing experiments
Rating standard: grade 0-no significant mold growth under magnifier; grade 1-the mold growth is rare or local, the coverage area on the sample surface is less than 10%; level 2-the coverage area of the mould on the surface of the sample is 10-30%; grade 3-the coverage area of the mould on the surface of the sample is 30-60%; grade 4-coverage area > 60% on sample surface.
Note that: the mildew-proof experiment is carried out by respectively grading 4 moulds, and the worst condition in the results, namely the condition that the mould coverage area is the largest, is taken as the final result.
As can be seen from tables 3 and 4, the detergents prepared in the embodiments 3 to 7 of the present invention have good sterilization and mildew prevention effects, the inhibition rate of Staphylococcus aureus after 10min can reach 94.22%, the inhibition rate of Escherichia coli after 10min can reach 84.52%, the mildew prevention grades are all 0 grade, no significant mold growth occurs under a magnifying glass, and the detergent is significantly superior to the detergents prepared in the comparative examples 1 to 4.
Compared with the example 7, the novel anionic-nonionic Gemini surfactant prepared in the example 2 is not added, and the sterilization effect and the mildew-proof effect of the novel anionic-nonionic Gemini surfactant are not greatly influenced compared with the example 7.
Compared with the example 7, the sterilization rate and the mildew-proof grade of the comparative example 2 are obviously reduced compared with the example 7 without adding lauric acid monoglyceride, and the lauric acid monoglyceride is a main bacteriostatic and mildew-proof active substance in the detergent.
Compared with example 7, the lauric acid monoglyceride is replaced by butyl p-hydroxybenzoate, and the butyl p-hydroxybenzoate has certain bacteriostatic and mildew-proof effects, but the effects are obviously inferior to those of the lauric acid monoglyceride.
Compared with the embodiment 7, the 5 wt% of hydrogen peroxide is replaced by the fluorescent whitening agent JD-3, wherein the 5 wt% of hydrogen peroxide also has certain mildew-proof and bacteriostatic effects, so that the sterilization rate and the mildew-proof grade are slightly reduced compared with the embodiment 7.
From the table, the clothes detergent containing the traditional Chinese medicine composition has the effects of mildew prevention, bacteria elimination and the like, the Aspergillus niger, Trichoderma viride, Penicillium funiculosum and Chaetomium globosum are selected for experiments, the mildew prevention grade reaches zero level, the sterilization rate of Staphylococcus aureus is more than 90%, the sterilization rate of Escherichia coli is more than 70%, two groups of data are subjected to test of a matched sample T, and the mean values have significant difference
Compared with the prior art, the novel anionic-nonionic Gemini surfactant synthesized by the invention is a novel surfactant integrating anionic, nonionic and Gemini surfactants, so that the novel anionic-nonionic Gemini surfactant has the advantages of the anionic and nonionic surfactants, is used at normal temperature, has strong detergency, good solubility, antistatic property, small irritation and the like, and has an unexpected technical effect of softness and has the beneficial effect of 1+1> 2.
The lauric acid monoglyceride is a nonionic surfactant, has good antibacterial, bactericidal, mildew-proof and emulsifying properties, is a natural preservative, is commonly used as a food mildew preventive, has the advantages of low cost, good bactericidal and preservative effects, safety, no irritation and the like, is applied to a linen detergent, has a synergistic effect with a novel anionic-nonionic Gemini type surfactant, can have an equivalent or even stronger washing effect under the condition of small dosage of the detergent when used at normal temperature, and reduces the cost of the detergent.
The 5 wt% of hydrogen peroxide added in the invention has bleaching and whitening effects, so that the linen is better white and beautiful, and the addition amount is lower, thus no irritation is caused;
the invention selects the surfactant which is easy to biodegrade for all components, is safe and environment-friendly, reaches and exceeds the sanitation and epidemic prevention standard of public textile washing in the public textile (linen) washing, has no phosphorus, toxicity or skin irritation compared with the traditional detergent, is simple and convenient to operate, is beneficial to the labor protection of workers, saves heat energy, saves electric power and water consumption, shortens the working time, improves the production efficiency, protects the quality of textile fibers, prolongs the service time of textiles, prolongs the service life of washing equipment, improves the comprehensive benefit by more than 25 percent, saves energy, reduces consumption and has obvious environment-friendly effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A multi-effect normal-temperature neutral liquid detergent is characterized by being prepared from the following raw materials: the novel anionic-nonionic Gemini surfactant comprises a novel anionic-nonionic Gemini surfactant, lauric monoglyceride, EDTA disodium, 5 wt% of hydrogen peroxide, plant essential oil, sodium citrate, sodium chloride and deionized water;
the novel anionic-nonionic Gemini surfactant has a structural formula shown in a formula I:
wherein R is1=CH3(CH2)11(OC2H4)23OH, and m is an integer of 5-18.
2. The multi-effect normal-temperature neutral liquid detergent as claimed in claim 1, which is prepared from the following raw materials in percentage by weight: 10-15% of novel anionic-nonionic Gemini surfactant, 3-7% of lauric acid monoglyceride, 1-3% of EDTA disodium, 1-3% of 5 wt% of hydrogen peroxide, 0.01-0.1% of vegetable essential oil, 5-12% of sodium citrate, 0.15-0.5% of sodium chloride and the balance of deionized water.
3. The multiple-effect normal-temperature neutral liquid detergent as claimed in claim 2, which is prepared from the following raw materials in percentage by weight: 12-14% of novel anionic-nonionic Gemini surfactant, 4-6% of lauric acid monoglyceride, 2-3% of EDTA disodium, 1.5-2.5% of 5 wt% of hydrogen peroxide, 0.05-0.09% of vegetable essential oil, 7-10% of sodium citrate, 0.25-0.45% of sodium chloride and the balance of deionized water.
4. The multi-effect normal-temperature neutral liquid detergent as claimed in claim 1, wherein the novel anionic-nonionic Gemini surfactant is prepared by the following method:
s1, synthesis of bromo-lauryl alcohol polyoxyethylene ether: adding excessive phosphorus tribromide into lauryl alcohol polyoxyethylene ether, standing for layering after reaction, and washing the upper layer until no pungent smell exists, wherein the upper layer is bromo-lauryl alcohol polyoxyethylene ether;
s2, synthesis of substituted benzene: adding anhydrous aluminum chloride into benzene, heating, adding bromo-lauryl alcohol polyoxyethylene ether, carrying out reduced pressure distillation after reaction to remove excessive benzene, and filtering to obtain substituted benzene;
s3, synthesis of substituted benzyl chloride: mixing paraformaldehyde, anhydrous zinc oxide and substituted benzene, introducing excessive hydrogen chloride gas, quenching reaction after the reaction, washing, drying, distilling under reduced pressure, and collecting the fraction at the temperature of 212-217 ℃ to obtain substituted benzyl chloride;
s4, synthesis of substituted benzyl polyoxyethylene ether alcohol: poly ethylene glycol with the structural formula of HO (C)2H4O)mH, m is an integer of 5-18, adding the mixture into a reactor, slowly adding metal sodium, slightly heating until the metal sodium is completely dissolved, adding substituted benzyl chloride, heating for reaction, and separating by column chromatography to obtain substituted benzyl polyoxyethylene ether alcohol;
s5, synthesizing a target product: after substituted benzyl polyoxyethylene ether alcohol reacts with chlorosulfonic acid, NaOH solution is added to adjust the pH value to be alkaline, and the solvent and water in the reaction system are removed under reduced pressure to obtain a target product, wherein the structure of the target product is shown as a formula I.
5. The multi-effect normal-temperature neutral liquid detergent as claimed in claim 4, wherein the ratio of the amounts of the polyoxyethylene lauryl ether and the phosphorus tribromide in step S1 is 1 (3-5); in the step S2, the mass ratio of the anhydrous aluminum chloride to the benzene to the brominated polyoxyethylene lauryl ether is (0.1-0.3): (10-15): 1; in the step S3, the mass ratio of the paraformaldehyde to the anhydrous zinc oxide to the substituted benzene is (5-10): (0.2-0.4): 1; the mass ratio of the polyethylene glycol, the metallic sodium and the substituted benzyl chloride in the step S4 is (1.1-1.3): (0.1-0.2): 1; the mass ratio of the substituted benzyl polyoxyethylene ether alcohol to chlorosulfonic acid in the step S5 is 1: (1.2-1.5), wherein the NaOH solution is a 10-15 wt% NaOH solution.
6. The multi-effect room temperature neutral liquid detergent of claim 1, wherein the plant essential oil is selected from lavender essential oil, rose essential oil, rosemary essential oil, lemon essential oil, bergamot essential oil, clove essential oil, mint essential oil, cinnamon essential oil, and thyme essential oil.
8. Use of the novel anionic-nonionic Gemini surfactant according to claim 7 in detergents.
9. A method for preparing the multi-effect normal temperature neutral liquid detergent as claimed in any one of claims 1-6, comprising the steps of: heating deionized water to 30-40 ℃, slowly adding EDTA disodium and sodium chloride, and stirring until the EDTA disodium and the sodium chloride are completely dissolved; cooling to 25-30 ℃, sequentially adding vegetable essential oil and 5 wt% of hydrogen peroxide, respectively stirring uniformly, cooling to room temperature, sequentially adding a novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride, and respectively stirring until the novel anionic-nonionic Gemini surfactant and lauric acid monoglyceride are completely dissolved; adding sodium citrate to adjust pH to neutral.
10. The method as claimed in claim 9, wherein the stirring speed is 300-1000 r/min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010208999.4A CN111286423A (en) | 2020-03-23 | 2020-03-23 | Multi-effect normal-temperature neutral liquid detergent and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010208999.4A CN111286423A (en) | 2020-03-23 | 2020-03-23 | Multi-effect normal-temperature neutral liquid detergent and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111286423A true CN111286423A (en) | 2020-06-16 |
Family
ID=71027552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010208999.4A Withdrawn CN111286423A (en) | 2020-03-23 | 2020-03-23 | Multi-effect normal-temperature neutral liquid detergent and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111286423A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115678688A (en) * | 2022-09-23 | 2023-02-03 | 深圳乙奇生物科技有限公司 | Special laundry detergent for sportswear and preparation method thereof |
CN115926900A (en) * | 2022-09-15 | 2023-04-07 | 营口理工学院 | A kind of multifunctional detergent for hotel linen and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101073757A (en) * | 2007-04-02 | 2007-11-21 | 中国科学院理化技术研究所 | Asymmetric Gemini surfactant and preparation method and application thereof |
CN101108327A (en) * | 2006-07-20 | 2008-01-23 | 中国科学院理化技术研究所 | Alkyl aryl benzyl polyoxyethylene ether anionic surfactant and its preparation method and application |
US8092595B1 (en) * | 2003-10-10 | 2012-01-10 | Sandia Corporation | Self-assembly of water-soluble nanocrystals |
CN102441338A (en) * | 2012-01-04 | 2012-05-09 | 西南石油大学 | A kind of sulfonate aralkyl anion-non-type gemini surfactant and its synthesis method |
CN104107664A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | High-interface-efficiency surfactant and preparation method thereof |
CN104818140A (en) * | 2015-04-30 | 2015-08-05 | 威莱(广州)日用品有限公司 | Antibacterial dishwashing detergent |
-
2020
- 2020-03-23 CN CN202010208999.4A patent/CN111286423A/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8092595B1 (en) * | 2003-10-10 | 2012-01-10 | Sandia Corporation | Self-assembly of water-soluble nanocrystals |
CN101108327A (en) * | 2006-07-20 | 2008-01-23 | 中国科学院理化技术研究所 | Alkyl aryl benzyl polyoxyethylene ether anionic surfactant and its preparation method and application |
CN101073757A (en) * | 2007-04-02 | 2007-11-21 | 中国科学院理化技术研究所 | Asymmetric Gemini surfactant and preparation method and application thereof |
CN102441338A (en) * | 2012-01-04 | 2012-05-09 | 西南石油大学 | A kind of sulfonate aralkyl anion-non-type gemini surfactant and its synthesis method |
CN104107664A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | High-interface-efficiency surfactant and preparation method thereof |
CN104818140A (en) * | 2015-04-30 | 2015-08-05 | 威莱(广州)日用品有限公司 | Antibacterial dishwashing detergent |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115926900A (en) * | 2022-09-15 | 2023-04-07 | 营口理工学院 | A kind of multifunctional detergent for hotel linen and preparation method thereof |
CN115926900B (en) * | 2022-09-15 | 2024-08-23 | 营口理工学院 | Multifunctional detergent for hotel linen and preparation method thereof |
CN115678688A (en) * | 2022-09-23 | 2023-02-03 | 深圳乙奇生物科技有限公司 | Special laundry detergent for sportswear and preparation method thereof |
CN115678688B (en) * | 2022-09-23 | 2024-03-01 | 深圳乙奇生物科技有限公司 | Special laundry detergent for sports clothes and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103343452B (en) | The efficient pre-treatment composite assistant of pure cotton fabric one-step method and preparation method | |
KR101128856B1 (en) | Environment-friendly solvent for water-cleaning and dry-cleaning, and composition for cleaning containing the same solvent | |
EP0201016A2 (en) | Builder-free liquid detergents with softening properties | |
CN102643724A (en) | Liquid laundry detergent containing tea saponin and method for preparing liquid laundry detergent | |
CN111286423A (en) | Multi-effect normal-temperature neutral liquid detergent and preparation method thereof | |
CN105002022A (en) | Low-temperature deoiling scouring agent and preparation method thereof | |
CN114746603B (en) | Soft base | |
CN104592527A (en) | Preparation method of modified silicone oil surfactant for textile | |
JPH03123634A (en) | Storage-stable aqueous wetting agent producing fewer bubbles in use | |
CN105255602A (en) | Degreasing laundry detergent | |
CN110724608A (en) | Neutral concentrated laundry detergent and preparation method thereof | |
WO2013186170A1 (en) | Detergent, cleaning agent, or pretreatment agent having greater cleaning power ii | |
CN108774891A (en) | A kind of cotton environment-friendly high-efficiency scouring agent and preparation method thereof | |
CN112625811A (en) | Novel low-temperature strong-effect oil stain emulsifier and preparation method thereof | |
WO2013160265A1 (en) | Laundry detergent, cleaning agent or washing liquid with improved sudsing behaviour | |
DE2427125C3 (en) | Foam-regulated detergents, cleaning agents and dishwashing detergents | |
CN105273859A (en) | Liquid laundry detergent capable of removing grease dirt | |
DE102009001973A1 (en) | Liquid bleach composition | |
CN109758059A (en) | A kind of stain removal bactericidal floor wet tissue and its preparation process | |
CN108441351A (en) | A kind of weaving degreaser | |
CN112646670A (en) | Novel low-temperature strong-effect oil stain emulsifier and preparation method thereof | |
JP2022102519A (en) | Soft base | |
CN105671950A (en) | Reactive anti-ultraviolet finishing agent for textiles | |
CN105462729A (en) | Novel laundry detergent | |
CN111068578B (en) | Surfactant, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200616 |
|
WW01 | Invention patent application withdrawn after publication |