CN114507206B - DL-alpha-tocopherol D-glucose amide nonionic surfactant and preparation method thereof - Google Patents
DL-alpha-tocopherol D-glucose amide nonionic surfactant and preparation method thereof Download PDFInfo
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- CN114507206B CN114507206B CN202210086691.6A CN202210086691A CN114507206B CN 114507206 B CN114507206 B CN 114507206B CN 202210086691 A CN202210086691 A CN 202210086691A CN 114507206 B CN114507206 B CN 114507206B
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- tocopherol
- glucamide
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- 239000002736 nonionic surfactant Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 title claims description 44
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 title claims description 41
- 239000011627 DL-alpha-tocopherol Substances 0.000 title claims description 41
- 229960000984 tocofersolan Drugs 0.000 title claims description 41
- -1 DL-alpha-tocopherol D-glucose amide Chemical class 0.000 title description 6
- 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 title description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 6
- 239000000182 glucono-delta-lactone Substances 0.000 claims description 6
- 229960003681 gluconolactone Drugs 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 33
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003995 emulsifying agent Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 235000011837 pasties Nutrition 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HTHCVJJDLCKIGB-UHFFFAOYSA-N CCO.CC1=CC=CC=C1.CC1=CC=CC=C1 Chemical compound CCO.CC1=CC=CC=C1.CC1=CC=CC=C1 HTHCVJJDLCKIGB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Chemical group OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical group OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 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 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RIVYDMWLVDWRRL-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CCOCC RIVYDMWLVDWRRL-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 125000002640 tocopherol group Chemical group 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a DL-alpha-tocopheryl D-glucamide nonionic surfactant and a preparation method thereof, wherein the surfactant is synthesized by taking DL-alpha-tocopheryl propylene oxide and di [2- (D-glucamide) ethyl ] amine as raw materials. It can be dissolved in most of organic solvent and water, can reduce the surface tension of system to a certain extent, is suitable for use as O/W type emulsifier, and can well reduce the surface tension of aqueous solution.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a novel DL-alpha-tocopherol D-glucose amide nonionic surfactant and a preparation method thereof.
Background
The traditional surfactant mainly takes petroleum base as raw material, and along with the excessive exploitation of coal and petroleum resources, energy resources are gradually in shortage, which restricts the development of the surfactant industry to a certain extent. Meanwhile, the traditional petrochemical products have serious pollution to the environment, are difficult to treat three wastes, are not environment-friendly and do not meet the requirement of sustainable development. Therefore, the search for new surfactants synthesized from alternative petroleum-based materials has become a necessary trend in the development of the surfactant industry. On the other hand, surfactants are widely used in foods, cosmetics, medicines and household cleaning products, and thus the safety of surfactants is also of great concern. Therefore, the research and development of the environment-friendly low-toxicity and easily biodegradable green surfactant prepared from natural renewable products as raw materials has important significance by comprehensively considering the availability of resources, the compatibility of the environment, the development sustainability of the surfactant industry and the safety of the surfactant. Traditional surfactants are difficult to biodegrade in natural environments (such as alkylphenol ethoxylates and sodium alkylbenzenesulfonate) and have adverse effects on aquatic organisms (such as phosphate), so development of green surfactants which are environment-friendly, low in toxicity and easy to biodegrade is imperative.
Vitamin E is a natural fat-soluble antioxidant, and has wide sources and low price, and the hydrolysate is tocopherol. The natural raw material DL-alpha-tocopherol is selected as the oil-philic end of the surfactant to replace nonylphenol for the synthesis of the surfactant and the research of technological routes. The surfactant prepared from the natural raw material DL-alpha-tocopherol has very excellent performance in pesticide preparations. (Instructions on agrology, 2020,22 (2): 270-276). H.Lipshutz et al report that such surfactants also facilitate a series of coupling reactions (e.g., suzuki-Miyaura coupling, negishi cross coupling, sonogashira coupling) in water, which can greatly reduce the amount of catalyst used .(J.Org.Chem.2012,77,3143-3148;J.Am.Chem.Soc.2012,134,49,19985–19988;Angew.Chem.Int.Ed.2021,60,4158-4163).
The lipophilic end of the nonionic surfactant is natural raw material DL-alpha-tocopherol, and the hydrophilic end is polyoxyethylene ether. Another green nonionic surfactant, alkyl glycoside (APG), is sugar-terminated hydrophilic and alkyl long chain-terminated lipophilic. Zhang Juan et al report the synthesis of a non-surfactant hydrophilic bis [2- (D-glucamidyl) ethylamine (bis [2- (D-glucamidyl) ethyl ] amine, chemical progress, 2011, 30:259-262). Compared with the traditional polyol type hydrophilic groups such as glycerol, pentaerythritol and sorbitol type di [2- (D-glucosamide) ethyl ] amine, the hydrophilic groups are more hydroxyl groups and are more hydrophilic. The raw material glucono-delta-lactone is a food additive, is cheap and easy to obtain, and is environment-friendly.
Therefore, aiming at a series of problems of low safety performance, poor biodegradability, large environmental hazard and the like of the surfactant prepared by taking nonrenewable petrochemical product nonylphenol as a raw material, the development of a green surfactant taking synthetic natural products as a raw material is very necessary.
Disclosure of Invention
In order to solve the problems, the invention provides a DL-alpha-tocopheryl D-glucamide nonionic surfactant and a preparation method thereof, wherein the surfactant is synthesized by taking DL-alpha-tocopheryl propylene oxide and di [2- (D-glucamide) ethyl ] amine as raw materials.
The invention provides a DL-alpha-tocopherol D-glucose amide nonionic surfactant and a preparation method thereof, wherein the surfactant can reduce the surface tension of a system to a certain extent, is suitable for being used as an O/W type emulsifier, and can well reduce the surface tension of an aqueous solution; the surfactant is simple and convenient, and is easy to realize industrial production.
The invention is realized in the following way:
a DL-alpha-tocopherol D-glucamide nonionic surfactant, the structure of which is represented by the following formula;
The preparation method of the DL-alpha-tocopherol D-glucamide nonionic surfactant comprises the following steps:
The reaction process is as follows: mixing DL-alpha-tocopheryl epoxypropane C and di [2- (D-glucosamide) ethyl ] amine D according to a mass ratio of 1:1.35-1.5, then adding DMSO (dimethyl sulfoxide) as a solvent, and carrying out reaction to obtain the surfactant.
Further, the reaction temperature is 80-90 ℃, and the stirring reaction is carried out for 8-10h.
Further, after the reaction was completed, the solvent was removed and recrystallized 3 times with petroleum ether to obtain a final product as a yellow pasty solid, DL- α -tocopherol D-glucamide.
Further, DL-alpha-tocopheryl propylene oxide C is synthesized by DL-alpha-tocopheryl A and epichlorohydrin B by the following procedure:
Namely, dissolving DL-alpha-tocopherol A and epichlorohydrin B by using an acetone solvent, uniformly stirring, then adding anhydrous K 2CO3 and tetrabutylammonium bromide as catalysts, reacting for 1h, and carrying out reflux reaction for 48h to obtain the DL-alpha-tocopheryl propylene oxide C.
Further, the DL-alpha-tocopherol A and epichlorohydrin are mixed according to the mass ratio of 1: 9.
Further, anhydrous K 2CO3 and tetrabutylammonium bromide are used as catalysts, and the reaction temperature is controlled to be 60 ℃ for 1 hour.
Further, the DL- α -tocopheryl propylene oxide C obtained by the reflux reaction was dried over anhydrous Na 2SO4 to filter out the organic phase, the solvent was removed by rotary evaporation, and the pure material was obtained by separation with a silica gel column chromatography (dichloromethane: petroleum ether=1:1).
Specifically, a certain amount of acetone solvent, 43 g of DL-alpha-tocopherol, 81.9 g (1:9 by mass) of epichlorohydrin and B are added into a 500mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod, and the mixture is stirred uniformly, and then a certain amount of anhydrous K 2CO3 and tetrabutylammonium bromide are added as catalysts to react for 1 hour at 60 ℃ and then reflux reaction is carried out for 48 hours. The organic phase was filtered off with anhydrous Na 2SO4, the solvent was removed by rotary evaporation and the pure material was obtained by separation on a column of chromatography silica gel (dichloromethane: petroleum ether=1:1) as DL- α -tocopheryl propylene oxide C.
The compound di [2- (D-glucosamide) ethyl ] amine D is synthesized by synthesizing diethylenetriamine E and glucono-delta-lactone F, and the preparation process is expressed as follows:
Adding diethylenetriamine E and gluconic acid-delta-lactone F into absolute ethyl alcohol, stirring for reaction, and obtaining the post-di [2- (D-glucosamide) ethyl ] amine after the reaction is finished.
Further, the reaction temperature was 35 ℃.
Further, after the reaction is completed, the product after the reaction is left to stand for a few minutes, is filtered by a buchner funnel, and is washed with absolute ethyl alcohol three times, so as to obtain white solid powder, namely the di [2- (D-glucosamide) ethyl ] amine.
Specifically, 2.515g of diethylenetriamine E,8.900g of glucono-delta-lactone F,60mL of absolute ethanol were placed in a three-necked flask equipped with a reflux condenser, thermometer and stirring bar, and stirred at 35 ℃. After the reaction is finished, the product is kept stand for a few minutes, is filtered by a buchner funnel, is washed by absolute ethyl alcohol for three times, and is obtained as white solid powder, namely the di [2- (D-glucosamide) ethyl ] amine D.
The invention has the beneficial effects that:
The invention discloses a DL-alpha-tocopherol D-glucamide nonionic surfactant which is synthesized by using DL-alpha-tocopherol, gluconic acid-delta-lactone, diethylenetriamine and epichlorohydrin as raw materials. It can be dissolved in most of organic solvent and water, can reduce the surface tension of system to a certain extent, is suitable for use as O/W type emulsifier, and can well reduce the surface tension of aqueous solution.
The surfactant prepared by the invention only needs to control the reaction temperature and time, is simple and convenient to synthesize, and is easy to realize industrial production.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the present invention.
Fig. 2 is a graph of gamma-CMC implemented in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The structure of the DL-alpha-tocopherol D-glucamide nonionic surfactant is shown as the following formula;
the preparation method of the DL-alpha-tocopherol D-glucamide nonionic surfactant is realized by the invention, and the preparation process is as follows:
The reaction process is as follows: mixing DL-alpha-tocopheryl epoxypropane C and di [2- (D-glucosamide) ethyl ] amine D according to a mass ratio of 1:1.35-1.5, then adding DMSO (dimethyl sulfoxide) as a solvent, and carrying out reaction to obtain the surfactant. The reaction temperature is 80-90 ℃, and the stirring reaction is carried out for 8-10h.
After the reaction is completed, the solvent is removed, petroleum ether is used for recrystallization for 3 times, and the final product is yellow pasty solid which is DL-alpha-tocopherol D-glucamide.
The process implemented is described in detail below in connection with specific embodiments.
Example 1:
DL-alpha-tocopheryl-epoxypropane and bis [2- (D-glucamidyl) ethyl ] amine in a 500mL three-necked flask equipped with reflux condenser, thermometer, stirring bar were used in an amount of 1:1.5 to 48.6 g of DL-alpha-tocopheryl propylene oxide, 68.9 g of bis [2- (D-glucamide) ethyl ] amine, 200ml of LDMSO as solvent was added and the mixture was stirred at 80℃for 10 hours. Removing the solvent, and recrystallizing with petroleum ether for 3 times to obtain the final product as yellow pasty solid. Purity is over 99% and yield is 60%.
Example 2:
DL-alpha-tocopheryl-epoxypropane and bis [2- (D-glucamidyl) ethyl ] amine in a 500mL three-necked flask equipped with reflux condenser, thermometer, stirring bar were used in an amount of 1:1.3 to the mixture was added 48.6 g of DL-. Alpha. -tocopheryl propylene oxide, 59.7 g of bis [2- (D-glucamide) ethyl ] amine, and 150ml of LDMSO as a solvent, followed by stirring at 90℃for 8 hours. Removing the solvent, and recrystallizing with petroleum ether for 3 times to obtain the final product as yellow pasty solid. Purity was 98% or more and yield was 62%.
Example 3:
DL-alpha-tocopheryl-epoxypropane and bis [2- (D-glucamidyl) ethyl ] amine in a 500mL three-necked flask equipped with reflux condenser, thermometer, stirring bar were used in an amount of 1:1.4 to the mixture was added 64.2 g of DL-. Alpha. -tocopheryl propylene oxide, 59.7 g of bis [2- (D-glucamide) ethyl ] amine, and 150ml of LDMSO as a solvent, followed by stirring at 82℃for 10 hours. Removing the solvent, and recrystallizing with petroleum ether for 3 times to obtain the final product as yellow pasty solid. Purity was 98.5% or more and yield was 63%.
Example 4:
DL-alpha-tocopheryl-epoxypropane and bis [2- (D-glucamidyl) ethyl ] amine in a 500mL three-necked flask equipped with reflux condenser, thermometer, stirring bar were used in an amount of 1:1.45 to the mixture was added 66.6 g of DL-. Alpha. -tocopheryl propylene oxide, 59.7 g of bis [2- (D-glucamide) ethyl ] amine, and 100ml of LDMSO as a solvent was added thereto, followed by stirring at 82℃for 10 hours. The solvent was removed and recrystallized 3 times from n-hexane to give the final product as a yellow pasty solid. Purity was 98.4% or more and yield was 64%.
Example 5:
DL-alpha-tocopheryl-epoxypropane and bis [2- (D-glucamidyl) ethyl ] amine in a 500mL three-necked flask equipped with reflux condenser, thermometer, stirring bar were used in an amount of 1:1.35 to which 62 g of DL-. Alpha. -tocopheryl propylene oxide and 59.7 g of bis [2- (D-glucamide) ethyl ] amine were added, 100ml of LDMSO was added as a solvent, and the mixture was stirred at 88℃for 10 hours. The solvent was removed and recrystallized 3 times from cyclohexane to give the final product as a yellow pasty solid. Purity was 98.4% or more and yield 67%.
The nuclear magnetic hydrogen spectrum of the compound DL-alpha-tocopherol D-glucamide nonionic surfactant is shown in figure 1, wherein:
1H NMR(500MHz,CH3OD)δ5.49(s,2H),4.42(ddd,J＝12.2,5.4,1.8Hz,2H),4.28–4.09(m,2H),3.99–3.65(m,6H),3.56–3.28(m,10H),3.15(s,2H),2.94–2.65(m,7H),2.57(s,2H),2.43–2.32(m,1H),2.24(td,J＝24.6,12.3Hz,1H),2.08(s,9H),2.02(dd,J＝24.8,12.2Hz,1H),1.94(d,J＝15.9Hz,2H),1.86–1.43(m,6H),1.39(s,2H),1.35–1.14(m,18H),0.90(dd,J＝12.6,10.0Hz,12H).13C NMR(125MHz,CH3OD)δ173.04(s),149.54(s),147.03(s),129.59(s),125.34(s),119.11(s),118.00(s),77.12(s),74.45(s),73.70(s),73.52(s),73.06(s),72.13(s),67.25(s),63.43(s),60.14(s),57.59(s),39.32(s),37.31(s),36.86(s),34.59(s),33.67(s),28.47(s),27.17(s),24.72(s),23.97(s),23.75(s),23.05(s),22.74(s),20.41(s),13.23(d,J＝12.5Hz).
The physicochemical properties of the DL-alpha-tocopherol D-glucamide-based nonionic surfactant are shown in the following table.
The first table shows the physical properties of DL-alpha-tocopherol D-glucamide, and the DL-alpha-tocopherol D-glucamide is an orange cream solid, has faint scent, is solid below 20 ℃ and is transparent liquid above 20 ℃.
TABLE 1
| Solvent(s) | Water and its preparation method | Ethanol | Toluene (toluene) | Petroleum ether | Dichloromethane (dichloromethane) | Tetrahydrofuran (THF) | Diethyl ether | Acetone (acetone) |
| Solubility of | Dissolving solution | Dissolving solution | Dissolving solution | Dissolving solution | Dissolving solution | Dissolving solution | Dissolving solution | Dissolving solution |
Dissolution Properties of Meter two, DL-alpha-tocopherol D-glucamide
As can be seen from tables 1 and 2, the surface speech agent is an orange yellow pasty solid at normal temperature, has a certain faint scent, is solid below 20 ℃ and is transparent liquid above 20 ℃. The surfactant is soluble in most organic solvents and water.
HLB value determination:
the calculation formula for the HLB value of the polyethylene glycol type (i.e., polyoxyethylene type) and the polyhydric alcohol type nonionic surfactant is:
by calculating the HLB value of the product to be 11.2, its aqueous solution was a stable milky dispersion, which was used as an O/W type emulsifier.
Cmc and surface tension measurements:
The surfactant product obtained in example 1 after four times of recrystallization refining purification is prepared into surfactant aqueous solution with concentration of 0.5-20mmol/L (a small amount of DMSO is added for dissolution assistance), the surface tension gamma of each solution with concentration of 0.5-20mmol/L at 25 ℃ is respectively measured, and corresponding gamma-CMC curves are drawn according to corresponding experimental data. Surface tension and cmc curves of the product CPA aqueous solution. As shown in fig. 2.
As can be seen from fig. 2, with the increasing concentration of the target product nonionic surfactant DL- α -tocopherol D-glucamide aqueous solution, the surface tension of the system is significantly reduced, and turning points appear when the concentration is low, here, the critical micelle concentration of the synthesized surfactant product, namely, cmc value. After the critical micelle concentration is reached, the surface tension of the system is basically kept at a certain value, and the change is small. The cmc value of the surfactant was 5mmol/L, which corresponds to a critical surface tension of 35.00mN/m, as can be read from the inflection point of the curve. Experimental data show that the synthesized product nonionic surfactant CPA can reduce the surface tension of the system to a certain extent, and provides a certain theoretical basis for the industrial application of the system.
Foam performance measurement:
foam stability test data are shown in table 3.
Table 3, foam stability test data
Experimental data show that the product has excellent foam performance, and the foam is rich, stable, durable, white and fine; good foamability and good foam stability.
In summary, the invention synthesizes a DL-alpha-tocopherol D-glucamide nonionic surfactant, which is synthesized by using DL-alpha-tocopherol, glucono-delta-lactone, diethylenetriamine and epichlorohydrin as raw materials. The synthesis is simple and convenient, and the industrial production is easy to realize. The structure is proved by nuclear magnetic hydrogen spectrum and carbon spectrum. It is soluble in most organic solvents and water. The surfactant HLB value was measured by some conventional physicochemical method to be about 11.2. The cmc value of the surfactant was 5mmol/L, and the critical surface tension was 35.70mN/m. Experimental data show that the synthesized product nonionic surfactant CPA can reduce the surface tension of the system to a certain extent, is suitable for being used as an O/W type emulsifier, and can well reduce the surface tension of aqueous solution.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A DL-alpha-tocopherol D-glucamide nonionic surfactant, the structure of which is represented by the following formula;
。
2. A process for preparing the DL-alpha-tocopherol D-glucamide-based nonionic surfactant according to claim 1, which comprises the following steps: mixing DL-alpha-tocopheryl epoxypropane and di [2- (D-glucosamide) ethyl ] amine according to a mass ratio of 1:1.35-1.5, then adding DMSO as solvent, and reacting to obtain DL-alpha-tocopherol D-glucamide.
3. The method for preparing DL-alpha-tocopherol D-glucamide based nonionic surfactant according to claim 2, wherein the reaction temperature is 80-90 ℃, and the stirring reaction is 8-10 h.
4. The method for preparing a DL- α -tocopherol D-glucamide-based nonionic surfactant according to claim 3, wherein after the completion of the reaction, the solvent is removed and the DL- α -tocopherol D-glucamide is recrystallized 3 times from petroleum ether.
5. The method for preparing the DL-alpha-tocopherol D-glucamide nonionic surfactant according to claim 2, wherein the DL-alpha-tocopheryl propylene oxide is synthesized by DL-alpha-tocopherol and epichlorohydrin, and the process is as follows: dissolving DL-alpha-tocopherol and epichlorohydrin by using an acetone solvent, uniformly stirring, adding anhydrous K 2CO3 and tetrabutylammonium bromide as catalysts, reacting 1h, and then refluxing 48 and h to obtain the DL-alpha-tocopheryl propylene oxide.
6. The preparation method of the DL-alpha-tocopherol D-glucamide nonionic surfactant according to claim 5, wherein the mass ratio of the DL-alpha-tocopherol to the epichlorohydrin is 1: 9.
7. The method for preparing a DL-alpha-tocopherol D-glucamide nonionic surfactant according to claim 6, wherein the anhydrous K 2CO3 and tetrabutylammonium bromide are used as catalysts, and the reaction temperature is controlled to be 1 h at 60 ℃.
8. The method for preparing a DL-alpha-tocopherol D-glucamide nonionic surfactant according to claim 7, wherein the DL-alpha-tocopheryl propylene oxide obtained by the reflux reaction is dried by anhydrous Na 2SO4 to filter out an organic phase, the solvent is removed by rotary evaporation, and the pure substance is obtained by separating by a chromatographic silica gel column.
9. The method for preparing DL-alpha-tocopherol D-glucamide nonionic surfactant according to claim 2, wherein the compound di [2- (D-glucamide) ethyl ] amine is prepared by synthesizing diethylenetriamine and glucono-delta-lactone, and the preparation process is expressed as: adding diethylenetriamine and glucono-delta-lactone into absolute ethyl alcohol, stirring for reaction, and obtaining di [2- (D-glucosamide) ethyl ] amine after the reaction is finished, wherein the reaction temperature is 35 ℃.
10. The method for preparing a DL-alpha-tocopherol D-glucamide nonionic surfactant according to claim 9, wherein after the reaction, the reaction product is left to stand for several minutes, and is suction-filtered with a buchner funnel and washed three times with absolute ethanol to obtain di [2- (D-glucamide) ethyl ] amine.
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| DL-α-生育酚聚乙二醇琥珀酸酯类非离子表面活性剂的合成及其在农药制剂中的应用;沈会杰等;《农药学学报》;第22卷(第2期);第270-276页 * |
| α-Tocopherol-based cationic amphiphiles with a novel pH sensitive hybrid linker for gene delivery，Muripiti, Venkanna等，National Institute of Technology;Muripiti, Venkanna等;《Organic & Biomolecular Chemistry》;第16卷(第16期);第 2932-2946页 * |
| 二[2-(D-葡萄糖酰胺基)乙基]胺的合成;张娟等;《化工进展》;第30卷(第S1期);第319-321页 * |
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