CN113698444B - Cationic alkyl glycoside quaternary ammonium salt surfactant and preparation process thereof - Google Patents
Cationic alkyl glycoside quaternary ammonium salt surfactant and preparation process thereof Download PDFInfo
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- 229930182470 glycoside Natural products 0.000 title claims abstract description 54
- -1 Cationic alkyl glycoside quaternary ammonium salt Chemical class 0.000 title claims abstract description 48
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 18
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical group CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims abstract description 16
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 16
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 16
- FHLZUEPKLGQEQP-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n,n-diethylpropan-1-amine Chemical compound CCN(CC)CCC[Si](C)(OC)OC FHLZUEPKLGQEQP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 239000012043 crude product Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 13
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003093 cationic surfactant Substances 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- 230000007928 solubilization Effects 0.000 abstract description 3
- 238000005063 solubilization Methods 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a cationic alkyl glycoside quaternary ammonium salt surfactant and a preparation process thereof, wherein 3-chloro-2-methyl propylene reacts with hypochlorous acid, then hydrogen chloride is removed to prepare an intermediate 1, then the intermediate 1 reacts with N, N-diethyl aminopropyl methyl dimethoxy silane to prepare an intermediate 2, the intermediate 2 reacts with dodecyl dimethyl tertiary amine hydrochloride to generate an intermediate 3, the intermediate 3 reacts with chloroacetyl chloride to prepare an intermediate 4, and finally the intermediate 4 reacts with alkyl glycoside to generate the cationic alkyl glycoside quaternary ammonium salt surfactant which has a quaternary ammonium salt structure, can be sterilized with high efficiency and has an antibacterial effect; in addition, the surfactant has an organosilicon structure and the characteristics of organic matters and inorganic matters, so that the surfactant has excellent high temperature resistance, and can play a role of organosilicon cationic surfactant and play a role of solubilization and emulsification.
Description
Technical Field
The invention belongs to the technical field of surfactant preparation, and particularly relates to a cationic alkyl glycoside quaternary ammonium salt surfactant and a preparation process thereof.
Background
The alkyl glycoside is a compound obtained by dehydration of glucose and fatty alcohol through acetal under the action of an acidic catalyst. The general composition is a mixture of mono-glycoside, di-glycoside, tri-glycoside and poly-glycoside, so that the alkyl polyglycoside is also called, and the alkyl polyglycoside belongs to a novel high-efficiency non-toxic biodegradable nonionic surfactant.
In recent years, the green safety of APG is well known, the irritation is extremely low, the biocompatibility is good, and the hydroxyl on the sugar ring in the alkyl glycoside can also react with various active groups to generate various APG derivatives. Meanwhile, the industrialized mature production of the alkyl glycoside promotes the synthesis development of the alkyl glycoside derivative, and the alkyl glycoside derivative not only maintains the advantages of the alkyl glycoside, but also obviously improves the water solubility, hard water resistance, foam stability, surface activity, antistatic performance and the like of the alkyl glycoside derivative through modification of the alkyl glycoside, wherein the cationic alkyl glycoside quaternary ammonium salt is one of the alkyl glycoside quaternary ammonium salts. The cationic alkyl glycoside quaternary ammonium salt not only has the excellent performance of a cationic surfactant, but also has the characteristics of no toxicity, small irritation and easy degradation, and simultaneously increases the synergistic effect of the cationic alkyl glycoside quaternary ammonium salt and the anionic surfactant, and is widely applied to the fields of cleaning agents, textile printing and dyeing, personal care, pesticides, antistatic agents, bactericides, industrial water treatment, drilling fluid treatment agents, foaming agents and the like.
However, the surfactant based on alkyl glycoside quaternary ammonium salt in the prior art has only excellent antibacterial performance, and does not have the excellent performances of high temperature resistance such as organic silicon and the like and solubilization and emulsification.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a cationic alkyl glycoside quaternary ammonium salt surfactant and a preparation process thereof.
The aim of the invention can be achieved by the following technical scheme:
A cationic alkyl glycoside quaternary ammonium surfactant comprising the steps of:
Firstly, adding mercury oxide into deionized water, controlling the temperature of the system to be not more than 30 ℃, introducing chlorine until the aqueous solution of the system turns light brown, magnetically stirring and dropwise adding 3-chloro-2-methyl propylene, controlling the dropwise adding time to be 1h, uniformly stirring until the aqueous solution of the system is colorless, introducing chlorine and controlling the temperature of the system to be not more than 50 ℃, preserving heat for 1h, cooling to 25-30 ℃, dropwise adding 35% sodium hydroxide aqueous solution with mass fraction to adjust the system to be neutral, continuously uniformly stirring for 1h to obtain a reaction solution, separating an organic layer and a water layer, extracting the water layer with diethyl ether three times, merging the obtained organic phase, drying, decompressing and distilling to obtain an intermediate 1;
In the first step, chlorine is introduced into deionized water to form hypochlorous acid in the presence of mercury oxide, then 3-chloro-2-methyl propylene is added, 3-chloro-2-methyl propylene reacts with hypochlorous acid, then sodium hydroxide is added to remove hydrogen chloride, and an intermediate 1 is prepared, wherein the process is as follows:
Introducing nitrogen into the three-neck flask to discharge air, then adding N, N-diethylaminopropyl methyl dimethoxy silane and absolute methanol, heating in a water bath at 45-55 ℃ and magnetically stirring, slowly adding the mixture a, stirring at a constant speed at the temperature and reacting for 6 hours, removing the methanol by rotary evaporation to obtain a crude product, eluting the crude product with absolute ethyl ether for 4 times, and then vacuum drying for 5 hours to obtain an intermediate 2;
In the second step, N-diethylaminopropyl methyl dimethoxy silane and the intermediate 1 are mixed under the nitrogen atmosphere by taking absolute methanol as a solvent to prepare an intermediate 2, and the reaction process is as follows:
Thirdly, adding dodecyl dimethyl tertiary amine hydrochloride and absolute ethyl alcohol into a four-necked flask, slowly adding the intermediate 2, controlling the temperature of a system to be 20-25 ℃ in the adding process, stirring at a constant speed, reacting for 6 hours to obtain a crude product, and carrying out reduced pressure distillation, cooling and suction filtration on the crude product to obtain an intermediate 3;
In the third step, dodecyl dimethyl tertiary amine hydrochloride and the intermediate 2 are mixed in absolute ethyl alcohol, and the dodecyl dimethyl tertiary amine hydrochloride and the intermediate 2 react to generate the intermediate 3, wherein the reaction process is as follows:
step four, adding the intermediate 3 prepared in the step three into tetrahydrofuran, stirring at a constant speed at room temperature, adding pyridine, transferring into ice water bath, adding chloroacetyl chloride, stirring at a constant speed, reacting for 4-6h, preparing an intermediate 4, and controlling the weight ratio of the intermediate 3 to the chloroacetyl chloride to the pyridine to be 1:1:0.03-0.05;
Step four, mixing the intermediate 3 and chloroacetyl chloride in tetrahydrofuran, adding pyridine as an organic base, and reacting the intermediate 3 and chloroacetyl chloride, wherein the reaction process is as follows:
and fifthly, adding the intermediate 4 and isopropanol prepared in the fourth step into a four-neck flask, uniformly stirring and heating to 70-80 ℃, adding alkyl glycoside, uniformly stirring and reacting for 6 hours to obtain a crude product, and performing rotary evaporation on the crude product under the conditions of the temperature of 65-70 ℃ and the pressure of 80kPa until the solvent is removed to obtain the cationic alkyl glycoside quaternary ammonium salt surfactant, wherein the dosage ratio of the intermediate 4, the isopropanol and the alkyl glycoside is 20.20-20.50 g:30 mL:105-110 g.
And fifthly, mixing the intermediate 4 and alkyl glycoside in isopropanol, and reacting the intermediate 4 and alkyl glycoside to generate the cationic alkyl glycoside quaternary ammonium salt surfactant, wherein the reaction process is as follows:
further, in the second step, the mixture a is formed by mixing the intermediate 1 and the absolute methanol according to the weight ratio of 1:10.
Further, the dosage ratio of mercury oxide, deionized water and 3-chloro-2-methyl propylene in the first step is 0.5-1 g:40 mL:50 mL.
Further, in the second step, the weight ratio of the N, N-diethylaminopropyl methyl dimethoxy silane to the mixture a is 1:10-15.
Further, in the third step, the dosage ratio of the dodecyl dimethyl tertiary amine hydrochloride, the intermediate 2 and the absolute ethyl alcohol is 17.00-17.25 g:6.25-6.30 g:50-75 mL.
The invention has the beneficial effects that:
In the preparation process, 3-chloro-2-methyl propylene reacts with hypochlorous acid, then hydrogen chloride is removed to prepare an intermediate 1, then the intermediate 2 reacts with N, N-diethyl aminopropyl methyl dimethoxy silane to prepare an intermediate 2, the intermediate 2 reacts with dodecyl dimethyl tertiary amine hydrochloride to prepare an intermediate 3, the intermediate 3 reacts with chloroacetyl chloride to prepare an intermediate 4, and finally the intermediate 4 reacts with alkyl glycoside to prepare the cationic alkyl glycoside quaternary ammonium surfactant. In addition, the surfactant has an organosilicon structure and the characteristics of organic matters and inorganic matters, so that the surfactant has excellent high temperature resistance, and can play a role of organosilicon cationic surfactant and play a role of solubilization and emulsification.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A cationic alkyl glycoside quaternary ammonium surfactant comprising the steps of:
Firstly, adding mercury oxide into deionized water, controlling the temperature of the system to be not more than 30 ℃, introducing chlorine until the aqueous solution of the system turns light brown, magnetically stirring and dropwise adding 3-chloro-2-methyl propylene, controlling the dropwise adding time to be 1h, uniformly stirring until the aqueous solution of the system is colorless, introducing chlorine and controlling the temperature of the system to be not more than 50 ℃, preserving heat for 1h, cooling to 25 ℃, dropwise adding 35% sodium hydroxide aqueous solution by mass percent to adjust the system to be neutral, continuously uniformly stirring for 1h, separating an organic layer and a water layer, extracting the water layer with diethyl ether for three times, combining the obtained organic phase, drying and distilling under reduced pressure to obtain an intermediate 1, wherein the dosage ratio of mercury oxide, deionized water and 3-chloro-2-methyl propylene is 0.5 g:40 mL/50 mL;
Introducing nitrogen into the three-neck flask to discharge air, then adding N, N-diethylaminopropyl methyl dimethoxy silane and absolute methanol, heating in a water bath at 45 ℃ and magnetically stirring, slowly adding a mixture a, stirring at a constant speed at the temperature and reacting for 6 hours, then removing methanol by rotary evaporation to obtain a crude product, eluting the crude product with absolute ethyl ether for 4 times, and then vacuum-drying for 5 hours to obtain an intermediate 2, N-diethylaminopropyl methyl dimethoxy silane and the mixture a in a weight ratio of 1:10;
the mixture a is formed by mixing an intermediate 1 and absolute methanol according to the weight ratio of 1:10.
Thirdly, adding dodecyl dimethyl tertiary amine hydrochloride and absolute ethyl alcohol into a four-necked flask, slowly adding the intermediate 2, controlling the temperature of a system to be 20 ℃ in the adding process, stirring at a constant speed, reacting for 6 hours to obtain a crude product, and carrying out reduced pressure distillation, cooling and suction filtration on the crude product to obtain the intermediate 3, wherein the dosage ratio of the dodecyl dimethyl tertiary amine hydrochloride to the intermediate 2 to the absolute ethyl alcohol is 17.00 g:6.25 g:50 mL;
Step four, adding the intermediate 3 prepared in the step three into tetrahydrofuran, stirring at a constant speed at room temperature, adding pyridine, transferring into ice water bath, adding chloroacetyl chloride, stirring at a constant speed, reacting for 4 hours, and preparing an intermediate 4, wherein the weight ratio of the intermediate 3 to the chloroacetyl chloride to the pyridine is controlled to be 1:1:0.03;
Adding the intermediate 4 and isopropanol prepared in the fourth step into a four-neck flask, uniformly stirring and heating to 70 ℃, adding alkyl glycoside, uniformly stirring and reacting for 6 hours to obtain a crude product, and performing rotary evaporation on the crude product under the conditions of the temperature of 65 ℃ and the pressure of 80kPa until the solvent is removed to obtain the cationic alkyl glycoside quaternary ammonium salt surfactant, wherein the dosage ratio of the intermediate 4 to the isopropanol to the alkyl glycoside is 20.20 g:30 mL:105 g.
Example 2
A cationic alkyl glycoside quaternary ammonium surfactant comprising the steps of:
Firstly, adding mercury oxide into deionized water, controlling the temperature of the system to be not more than 30 ℃, introducing chlorine until the aqueous solution of the system turns light brown, magnetically stirring and dropwise adding 3-chloro-2-methyl propylene, controlling the dropwise adding time to be 1h, uniformly stirring until the aqueous solution of the system is colorless, introducing chlorine and controlling the temperature of the system to be not more than 50 ℃, preserving heat for 1h, cooling to 25 ℃, dropwise adding 35% sodium hydroxide aqueous solution by mass percent to adjust the system to be neutral, continuously uniformly stirring for 1h, separating an organic layer and a water layer, extracting the water layer with diethyl ether for three times, combining the obtained organic phase, drying and distilling under reduced pressure to obtain an intermediate 1, wherein the dosage ratio of mercury oxide, deionized water and 3-chloro-2-methyl propylene is 0.81 g:40 mL/50 mL;
Introducing nitrogen into the three-neck flask to discharge air, then adding N, N-diethylaminopropyl methyl dimethoxy silane and absolute methanol, heating in a water bath at 45 ℃ and magnetically stirring, slowly adding a mixture a, stirring at a constant speed at the temperature and reacting for 6 hours, then removing methanol by rotary evaporation to obtain a crude product, eluting the crude product with absolute ethyl ether for 4 times, and then vacuum-drying for 5 hours to obtain an intermediate 2, N-diethylaminopropyl methyl dimethoxy silane and the mixture a in a weight ratio of 1:10;
the mixture a is formed by mixing an intermediate 1 and absolute methanol according to the weight ratio of 1:10.
Thirdly, adding dodecyl dimethyl tertiary amine hydrochloride and absolute ethyl alcohol into a four-necked flask, slowly adding the intermediate 2, controlling the temperature of a system to be 20 ℃ in the adding process, stirring at a constant speed, reacting for 6 hours to obtain a crude product, and carrying out reduced pressure distillation, cooling and suction filtration on the crude product to obtain the intermediate 3, wherein the dosage ratio of the dodecyl dimethyl tertiary amine hydrochloride to the intermediate 2 to the absolute ethyl alcohol is 17.05 g:6.28 g:60 mL;
Step four, adding the intermediate 3 prepared in the step three into tetrahydrofuran, stirring at a constant speed at room temperature, adding pyridine, transferring into ice water bath, adding chloroacetyl chloride, stirring at a constant speed, reacting for 4 hours, and preparing an intermediate 4, wherein the weight ratio of the intermediate 3 to the chloroacetyl chloride to the pyridine is controlled to be 1:1:0.03;
Adding the intermediate 4 and isopropanol prepared in the fourth step into a four-neck flask, uniformly stirring and heating to 70 ℃, adding alkyl glycoside, uniformly stirring and reacting for 6 hours to obtain a crude product, and performing rotary evaporation on the crude product under the conditions of the temperature of 65 ℃ and the pressure of 80kPa until the solvent is removed to obtain the cationic alkyl glycoside quaternary ammonium salt surfactant, wherein the dosage ratio of the intermediate 4 to the isopropanol to the alkyl glycoside is 20.30 g:30 mL:105 g.
Example 3
A cationic alkyl glycoside quaternary ammonium surfactant comprising the steps of:
Firstly, adding mercury oxide into deionized water, controlling the temperature of the system to be not more than 30 ℃, introducing chlorine until the aqueous solution of the system turns light brown, magnetically stirring and dropwise adding 3-chloro-2-methyl propylene, controlling the dropwise adding time to be 1h, uniformly stirring until the aqueous solution of the system is colorless, introducing chlorine and controlling the temperature of the system to be not more than 50 ℃, preserving heat for 1h, then cooling to 30 ℃, dropwise adding 35% sodium hydroxide aqueous solution by mass percent to adjust the system to be neutral, continuously uniformly stirring for 1h, separating an organic layer and a water layer, extracting the water layer with diethyl ether for three times, combining the obtained organic phases, drying and distilling under reduced pressure to obtain an intermediate 1, wherein the dosage ratio of the mercury oxide, the deionized water and the 3-chloro-2-methyl propylene is 0.8 g:40 mL/50 mL;
Introducing nitrogen into the three-neck flask to discharge air, then adding N, N-diethylaminopropyl methyl dimethoxy silane and absolute methanol, heating in a water bath at 55 ℃ and magnetically stirring, slowly adding the mixture a, stirring at a constant speed at the temperature and reacting for 6 hours, then removing the methanol by rotary evaporation to obtain a crude product, eluting the crude product with absolute ethyl ether for 4 times, and then vacuum-drying for 5 hours to obtain an intermediate 2, wherein the weight ratio of the N, N-diethylaminopropyl methyl dimethoxy silane to the mixture a is 1:15;
the mixture a is formed by mixing an intermediate 1 and absolute methanol according to the weight ratio of 1:10.
Thirdly, adding dodecyl dimethyl tertiary amine hydrochloride and absolute ethyl alcohol into a four-necked flask, slowly adding the intermediate 2, controlling the temperature of a system to be 25 ℃ in the adding process, stirring at a constant speed, reacting for 6 hours to obtain a crude product, and carrying out reduced pressure distillation, cooling and suction filtration on the crude product to obtain the intermediate 3, wherein the dosage ratio of the dodecyl dimethyl tertiary amine hydrochloride to the intermediate 2 to the absolute ethyl alcohol is 17.25 g:6.28 g:70 mL;
step four, adding the intermediate 3 prepared in the step three into tetrahydrofuran, stirring at a constant speed at room temperature, adding pyridine, transferring into ice water bath, adding chloroacetyl chloride, stirring at a constant speed, reacting for 6 hours, and preparing an intermediate 4, wherein the weight ratio of the intermediate 3 to the chloroacetyl chloride to the pyridine is controlled to be 1:1:0.04;
Adding the intermediate 4 and isopropanol prepared in the fourth step into a four-neck flask, uniformly stirring and heating to 80 ℃, adding alkyl glycoside, uniformly stirring and reacting for 6 hours to obtain a crude product, and performing rotary evaporation on the crude product under the conditions of the temperature of 70 ℃ and the pressure of 80kPa until the solvent is removed to obtain the cationic alkyl glycoside quaternary ammonium salt surfactant, wherein the dosage ratio of the intermediate 4 to the isopropanol to the alkyl glycoside is 20.40 g:30 mL:1110 g.
Example 4
A cationic alkyl glycoside quaternary ammonium surfactant comprising the steps of:
Firstly, adding mercury oxide into deionized water, controlling the temperature of the system to be not more than 30 ℃, introducing chlorine until the aqueous solution of the system turns light brown, magnetically stirring and dropwise adding 3-chloro-2-methyl propylene, controlling the dropwise adding time to be 1h, uniformly stirring until the aqueous solution of the system is colorless, introducing chlorine and controlling the temperature of the system to be not more than 50 ℃, preserving heat for 1h, then cooling to 30 ℃, dropwise adding 35% sodium hydroxide aqueous solution with mass fraction to adjust the system to be neutral, continuously uniformly stirring for 1h, separating an organic layer and a water layer, extracting the water layer with diethyl ether for three times, combining the obtained organic phases, drying and distilling under reduced pressure to obtain an intermediate 1, wherein the dosage ratio of the mercury oxide, the deionized water and the 3-chloro-2-methyl propylene is 1 g:40 mL:50 mL;
Introducing nitrogen into the three-neck flask to discharge air, then adding N, N-diethylaminopropyl methyl dimethoxy silane and absolute methanol, heating in a water bath at 55 ℃ and magnetically stirring, slowly adding the mixture a, stirring at a constant speed at the temperature and reacting for 6 hours, then removing the methanol by rotary evaporation to obtain a crude product, eluting the crude product with absolute ethyl ether for 4 times, and then vacuum-drying for 5 hours to obtain an intermediate 2, wherein the weight ratio of the N, N-diethylaminopropyl methyl dimethoxy silane to the mixture a is 1:15;
the mixture a is formed by mixing an intermediate 1 and absolute methanol according to the weight ratio of 1:10.
Thirdly, adding dodecyl dimethyl tertiary amine hydrochloride and absolute ethyl alcohol into a four-necked flask, slowly adding the intermediate 2, controlling the temperature of a system to be 25 ℃ in the adding process, stirring at a constant speed, reacting for 6 hours to obtain a crude product, and carrying out reduced pressure distillation, cooling and suction filtration on the crude product to obtain the intermediate 3, wherein the dosage ratio of the dodecyl dimethyl tertiary amine hydrochloride to the intermediate 2 to the absolute ethyl alcohol is 17.25 g:6.30 g:75 mL;
Step four, adding the intermediate 3 prepared in the step three into tetrahydrofuran, stirring at a constant speed at room temperature, adding pyridine, transferring into ice water bath, adding chloroacetyl chloride, stirring at a constant speed, reacting for 6 hours, and preparing an intermediate 4, wherein the weight ratio of the intermediate 3 to the chloroacetyl chloride to the pyridine is controlled to be 1:1:0.05;
Adding the intermediate 4 and isopropanol prepared in the fourth step into a four-neck flask, uniformly stirring and heating to 80 ℃, adding alkyl glycoside, uniformly stirring and reacting for 6 hours to obtain a crude product, and performing rotary evaporation on the crude product under the conditions of the temperature of 70 ℃ and the pressure of 80kPa until the solvent is removed to obtain the cationic alkyl glycoside quaternary ammonium salt surfactant, wherein the dosage ratio of the intermediate 4 to the isopropanol to the alkyl glycoside is 20.50 g:30 mL:110 g.
Comparative example 1
The comparative example is an alkyl glycoside quaternary ammonium salt surfactant synthesized by alkyl glycoside and a cationic etherifying agent in the prior art.
Antibacterial Properties and comparison of examples 1-4 and comparative example 1
From the above table, it can be seen that the antibacterial rate of examples 1-4 against E.coli is 99.5-99.7%, the antibacterial rate against Staphylococcus aureus is 96.3-97.5%, and the critical micelle concentration is 2.0-2.2mmol/L; comparative example 1 has a bacteriostatic rate of 98.5% for E.coli, 95.2% for Staphylococcus aureus, and a critical micelle concentration of 2.5mmol/L.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (2)
1. The preparation process of the cationic alkyl glycoside quaternary ammonium salt surfactant is characterized by comprising the following steps of:
Firstly, adding mercury oxide into deionized water, controlling the temperature of the system to be not more than 30 ℃, introducing chlorine gas, magnetically stirring, dropwise adding 3-chloro-2-methyl propylene, controlling the dropwise adding time to be 1h, uniformly stirring until the aqueous solution of the system is colorless, introducing the chlorine gas, controlling the system to be not more than 50 ℃, preserving heat for 1h at the temperature, cooling to 25-30 ℃, dropwise adding 35% sodium hydroxide aqueous solution with mass fraction, regulating the system to be neutral, continuously uniformly stirring for 1h, preparing a reaction solution, separating an organic layer and a water layer, extracting the water layer for three times, merging the obtained organic phase, drying, and distilling under reduced pressure to obtain an intermediate 1;
Introducing nitrogen into the three-neck flask to discharge air, then adding N, N-diethylaminopropyl methyl dimethoxy silane and absolute methanol, heating in a water bath at 45-55 ℃ and magnetically stirring, slowly adding the mixture a, stirring at a constant speed at the temperature and reacting for 6 hours, removing the methanol by rotary evaporation to obtain a crude product, eluting the crude product with absolute ethyl ether for 4 times, and then vacuum drying for 5 hours to obtain an intermediate 2;
Thirdly, adding dodecyl dimethyl tertiary amine hydrochloride and absolute ethyl alcohol into a four-necked flask, slowly adding the intermediate 2, controlling the temperature of a system to be 20-25 ℃ in the adding process, stirring at a constant speed, reacting for 6 hours to obtain a crude product, and carrying out reduced pressure distillation, cooling and suction filtration on the crude product to obtain an intermediate 3;
step four, adding the intermediate 3 prepared in the step three into tetrahydrofuran, stirring at a constant speed at room temperature, adding pyridine, transferring into ice water bath, adding chloroacetyl chloride, stirring at a constant speed, reacting for 4-6h, preparing an intermediate 4, and controlling the weight ratio of the intermediate 3 to the chloroacetyl chloride to the pyridine to be 1:1:0.03-0.05;
Fifthly, adding the intermediate 4 and isopropanol prepared in the fourth step into a four-neck flask, stirring at a constant speed and heating to 70-80 ℃, adding dodecyl glycoside, stirring at a constant speed and reacting for 6 hours to obtain a crude product, and performing rotary evaporation on the crude product under the conditions of the temperature of 65-70 ℃ and the pressure of 80kPa until the solvent is removed to obtain the cationic dodecyl glycoside quaternary ammonium salt surfactant, wherein the dosage ratio of the intermediate 4, the isopropanol and the alkyl glycoside is (20.20-20.50) g to 30mL to (105-110);
the mixture a is formed by mixing an intermediate 1 and absolute methanol according to the weight ratio of 1:10;
The dosage ratio of the mercury oxide, the deionized water and the 3-chloro-2-methyl propylene is (0.5-1) g:40 mL:50 mL;
In the second step, the weight ratio of the N, N-diethylaminopropyl methyl dimethoxy silane to the mixture a is 1:10-15;
in the third step, the dosage ratio of the dodecyl dimethyl tertiary amine hydrochloride, the intermediate 2 and the absolute ethyl alcohol is (17.00-17.25) g to (6.25-6.30) g to 50-75mL.
2. A cationic alkyl glycoside quaternary ammonium salt surfactant, characterized in that the cationic alkyl glycoside quaternary ammonium salt surfactant is prepared by the preparation process of the cationic alkyl glycoside quaternary ammonium salt surfactant according to claim 1.
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