CN114276272B - Method for producing fullerene water-soluble derivative and recovering triethanolamine oxide - Google Patents
Method for producing fullerene water-soluble derivative and recovering triethanolamine oxide Download PDFInfo
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Abstract
The invention discloses a method for producing fullerene water-soluble derivatives and recovering triethanolamine oxide, belonging to the technical field of fine chemical engineering. The method comprises the following steps: mixing triethanolamine with fullerene and chromium trioxide, adding carbon tetrachloride solution for reaction, adding water after the reaction is finished, stirring, standing, separating liquid to obtain a water layer, adding a precipitator, enabling oily liquid to appear at the bottom of the solution, standing, separating liquid to obtain a lower-layer oil phase, adding water into the oil phase for dissolving, adding the carbon tetrachloride solution, standing, separating liquid, drying an uppermost-layer oil layer to obtain the recovered triethanolamine, and enabling a bottom layer to be a fullerene water-soluble derivative, wherein the precipitator is one or more of isopropanol and n-hexane. The method is simple and efficient, the obtained triethanolamine oxide has higher purity, can be used as a raw material for secondary reaction, solves the problem that the triethanolamine oxide cannot be recycled in a complex environment, and has wide application prospect.
Description
Technical Field
The invention relates to a method for producing fullerene water-soluble derivatives and recovering triethanolamine oxide, belonging to the technical field of fine chemical engineering.
Background
Fullerene is a cage-shaped molecule completely composed of carbon, is a unique allotrope in a plurality of carbon nano materials, and has the excellent characteristics of high reaction activity, strong oxidation resistance and the like. However, intrinsic fullerenes have a relatively strong hydrophobicity and are soluble only in limited organic solvents (e.g., benzene, carbon tetrachloride, etc.). It is therefore often desired to better perform the function of intrinsic fullerenes by grafting functional groups thereon to obtain fullerene derivatives having good water solubility, and to be applied in the fields of cosmetics, biological medicine, etc.
The triethanolamine oxide is a product obtained by oxidizing triethanolamine. The structural sign is N-O polar group. Because of the excellent characteristics of no harm to human bodies, extremely easy water dissolution, antibacterial property and the like, the water-soluble polyurethane foam is increasingly regarded as a green, safe and extremely promising chemical raw material. The triethanolamine oxide group is combined with the intrinsic fullerene in a grafting way to synthesize the fullerene derivative with good water solubility.
However, because the triethanolamine is a viscous liquid at normal temperature, the triethanolamine is extremely soluble in water, the boiling point is up to 360 ℃, and when the triethanolamine is used as a reaction raw material for synthesizing the fullerene water-soluble derivative, a large amount of viscous triethanolamine is still often left to be mixed with the target product of the water-soluble fullerene derivative after conventional distillation for water removal; if the temperature is further increased, the structure of the fullerene derivative is destroyed. Therefore, how to effectively separate the fullerene derivative from the triethanolamine oxide in a complex reaction system containing the fullerene remains a challenge, and is one of the key problems of further purifying the fullerene and recycling the triethanolamine oxide.
Disclosure of Invention
[ technical problem ]
At present, no better method is available for effectively separating the fullerene derivative from the triethanolamine, and the recovery and the reutilization of the triethanolamine cannot be realized.
Technical scheme
In order to solve the above problems, the present invention provides a method for recovering triethanolamine oxide under a fullerene-containing water-soluble derivative system, the method comprising: mixing triethanolamine oxide with fullerene and chromium trioxide according to a certain proportion, adding carbon tetrachloride solution for mixing and reacting, adding water after the reaction is finished, stirring, standing for the first time, and separating liquid to obtain an upper water layer; adding a precipitant into the obtained water layer, wherein oily liquid appears at the bottom of the solution, standing for the second time, separating liquid, taking a lower-layer oil phase, adding water into the taken oil phase for dissolution, adding a carbon tetrachloride solution, standing for the third time, separating liquid, drying the uppermost-layer oil layer to obtain the recovered triethanolamine oxide, and obtaining the fullerene water-soluble derivative as the bottom layer, wherein the precipitant is one or more of isopropanol and n-hexane.
In one embodiment of the present invention, the method for preparing the triethanolamine oxide comprises the following steps: dissolving triethanolamine in water, preparing to obtain triethanolamine water solution, adding a catalyst, heating to a certain temperature, adding hydrogen peroxide, performing heat preservation treatment, heating after a period of heat preservation, performing reaction, adding sodium persulfate after the reaction is finished, and standing; and then carrying out rotary distillation on the reaction solution, taking the solution after rotary distillation, standing until the solution is layered, taking an upper liquid phase from the separated solution, and drying to obtain the triethanolamine oxide.
In one embodiment of the present invention, in the process for the preparation of triethanolamine oxide, triethanolamine: molar ratio of hydrogen peroxide=1:1.1 to 1:2.
In one embodiment of the invention, in the preparation method of the triethanolamine oxide, the heat preservation treatment temperature is 40-65 ℃, the time is 0.5-1 h, the temperature is raised to 75-90 ℃ after heat preservation, and the reaction time is 3-4h.
In one embodiment of the invention, in the preparation method of the triethanolamine oxide, the catalyst is one or more of trisodium citrate, sodium citrate and EDTA disodium salt.
In one embodiment of the invention, in the preparation method of the triethanolamine oxide, when the catalyst is selected from a plurality of mixtures, the optimal ratio of the substances of trisodium citrate, sodium citrate and EDTA disodium salt is 1:1:1.
In one embodiment of the invention, in the preparation method of the triethanolamine oxide, sodium persulfate is added and kept stand to be a single uniform colorless to pale yellow solution.
In one embodiment of the present invention, in the method for preparing triethanolamine oxide, the temperature in the rotary distillation is set to 48-55deg.C for 20-30min.
In one embodiment of the invention, in the preparation method of the triethanolamine oxide, the upper layer is colorless to yellow viscous liquid phase after spin evaporation and standing, and the lower layer is white solid.
In one embodiment of the invention, the triethanolamine oxide: fullerene: chromium trioxide molar ratio = 50-150:1:10-30.
In one embodiment of the invention, the first resting stage is stratified into an upper tan liquid phase and a lower violet liquid phase.
In one embodiment of the invention, when two mixtures are selected as precipitants, the volume ratio of isopropanol to n-hexane is 3:5 to 9:5, wherein isopropanol is preferred: the volume ratio of n-hexane is 7:5 to 9:5, most preferably 7:5.
In one embodiment of the invention, the second standing is stratified into an upper colorless liquid phase and a lower tan liquid phase.
In one embodiment of the present invention, the third standing delamination is an upper yellow liquid phase, a middle layer is a colorless or purple liquid phase, and a lower layer is a black precipitate.
In one embodiment of the present invention, the drying is performed to remove residual water from the triethanolamine oxide at a temperature of 50-70 ℃ for 10-30 min.
In one embodiment of the present invention, the first addition of carbon tetrachloride: adding water for the first time: adding water for the second time: the volume ratio of carbon tetrachloride added for the second time is = (1-5): (1-5).
In one embodiment of the invention, the mass concentration of the fullerene derivative in the mixed solution is 0.1-0.2mg/mL; the optimal concentration is 0.13mg/mL.
In one embodiment of the present invention, the method specifically comprises the following steps:
(1) Dissolving triethanolamine in water, preparing to obtain a triethanolamine water solution, adding a catalyst, heating, and performing heat preservation treatment; hydrogen peroxide is added after the temperature is maintained for a period of time, and the reaction is carried out after the temperature is raised; adding sodium persulfate after the reaction is finished, and standing; then carrying out rotary distillation on the reaction solution, taking a solution after rotary distillation, standing until the solution is layered, and separating the solution to obtain an upper liquid phase to obtain a triethanolamine oxide product;
(2) Mixing the obtained triethanolamine oxide with fullerene and chromium trioxide according to a certain proportion, and then adding carbon tetrachloride solution for mixing and reacting; adding water after the reaction, stirring, standing, separating liquid, and taking an upper water layer; adding a precipitant into the obtained water layer, wherein oily liquid appears at the bottom of the solution; standing and separating to obtain lower oil phase, adding water to dissolve, adding carbon tetrachloride solution, standing, separating to obtain uppermost oil layer, oven drying to obtain recovered triethanolamine oxide product, and collecting fullerene water-soluble derivative as bottom layer.
In one embodiment of the invention, the triethanolamine yield is 95%, the post reaction recovery is 87% and the purity is 95%.
The invention also provides application of the method in the field of chemical industry.
The beneficial effects of the invention are that
The invention provides a method for separating and recovering triethanolamine oxide in a complex system of fullerene water-soluble derivatives. The recovered triethanolamine oxide can be recycled and put into the next reaction production, the yield of triethanolamine is 95%, the recovery rate after the reaction is 87%, and the purity is 95%, so that the raw material utilization rate is greatly improved, and the production cost can be saved. The method can also well separate and obtain the fullerene derivative.
Drawings
FIG. 1 is an infrared (FT-IR) spectrum of triethanolamine oxide.
FIG. 2 is a High Performance Liquid Chromatography (HPLC) diagram of triethanolamine oxide, wherein, (a) is an HPLC diagram of the prepared triethanolamine oxide; (b) HPLC spectrum of the recovered triethanolamine oxide.
FIG. 3 is a schematic diagram of the structural formulas of triethanolamine and fullerene derivatives and the preparation of fullerene derivatives.
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) of the recovered triethanolamine oxide.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings. The raw materials mentioned in the invention are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all those familiar to the person skilled in the art.
Example 1 preparation and recovery of triethanolamine oxide
(1) Preparation of triethanolamine oxide
5mL of triethanolamine and 3.3mL of hydrogen peroxide were measured (molar ratio of triethanolamine to hydrogen peroxide=1:1.1). Triethanolamine was first added to a three-necked flask and dissolved by adding 25mL of water. 0.258g of trisodium citrate was added and the temperature was raised to 60 ℃. And (3) quickly adding hydrogen peroxide after the temperature reaches 60 ℃, stirring, and preserving the heat for 1h. Heating to 75-80 deg.c for reaction for 3.5 hr and stirring.
After the reaction was completed, 0.63g of excess sodium persulfate was added to remove excess hydrogen peroxide, and the mixture was allowed to stand for 2 hours. And (3) carrying out rotary evaporation on the reaction liquid to remove water, taking a rotary evaporated solution, standing for 12 hours, layering the solution, separating the solution, taking an upper yellow oil phase, and drying to obtain a final product.
The obtained triethanolamine is subjected to infrared spectrum scanning, and the result is shown in figure 1, and the spectrum of the obtained triethanolamine is 3371.925cm -1 Vibration absorption peak of-OH was present at 2962.125cm -1 Where there is-CH 2 -a stretching vibration peak at 2887.88cm -1 Where there is-CH 2 -a stretching vibration peak at 1443.458cm -1 Where there is-CH 2 Bending vibration peak at 1381.747cm -1 、1220.72cm -1 There was a C-N stretching vibration peak at 1047.158cm -1 、940.127cm -1 There is a stretching vibration peak of N-O, thus verifying successful synthesis of triethanolamine oxide.
The result of high performance liquid chromatography analysis of the prepared triethanolamine oxide is shown in fig. 2 (a), and the peak of the triethanolamine oxide exists at 2.170min, the peak area is 306.6278 mAU min, and the purity is 97%.
(2) Separation and recovery of triethanolamine oxide under fullerene-containing water-soluble derivative system:
2mL of triethanolamine oxide, 0.1g of fullerene and 0.42g of chromium trioxide are measured, 5mL of carbon tetrachloride is added for dissolution, and the reaction is stirred for 6 hours at 25 ℃. The reaction-completed solution became a dark brown blackish solution. Taking the solution after the reaction, adding 5mL of deionized water, vigorously stirring, standing, and separating a liquid and water layer (containing fullerene derivative, triethanolamine oxide and trivalent chromium ions). After adding the precipitant (70 mL isopropanol +50mL n-hexane), oily liquid (triethanolamine oxide, fullerene derivative) appeared at the bottom of the solution. Standing and separating to obtain oily liquid, adding 5mL of deionized water into the oily liquid for dissolution, adding 20mL of carbon tetrachloride solution, standing, separating, drying the uppermost oil layer to obtain the recovered triethanolamine oxide, and obtaining the fullerene water-soluble derivative as the bottom layer.
The structural formula of the triethanolamine oxide and the fullerene water-soluble derivative and the preparation schematic diagram of the fullerene derivative are shown in figure 3.
The recovered triethanolamine oxide was subjected to X-ray photoelectron spectroscopy, and the result was shown in FIG. 4, in which the Cr 2p spectrum showed a peak at 584.05eV, and the content was estimated to be 0.2% based on the peak area.
The obtained triethanolamine was subjected to high performance liquid chromatography, and as shown in fig. 2 (b), a peak of the triethanolamine was found to exist at 2.173min, the peak area was 274.21mau min, and the purity was 95%.
The above data all indicate the synthesis of triethanolamine oxide with a preparation yield of 95% and a purity of 97%. The recovery rate is 87% and the purity is 95%.
The data show that the triethanolamine is successfully prepared, the triethanolamine can be effectively recovered after the reaction, and the recovered triethanolamine has high purity.
Example 2
Referring to example 1, triethanolamine was varied: the mole ratio of hydrogen peroxide and other conditions are unchanged, thus preparing the triethanolamine oxide, and separating and recycling the triethanolamine oxide in a fullerene derivative-containing system. The specific results are shown in Table 1, and it can be seen that when triethanolamine: when the molar ratio of the hydrogen peroxide is 1:1-2, the yield of the triethanolamine can be more than 90%, the recovery rate of the final triethanolamine can be more than 80%, the purity of the recovered triethanolamine is more than 90%, and the effective recovery and utilization of the triethanolamine can be realized.
TABLE 1 recovery effect of triethanolamine and Hydrogen peroxide at different molar ratios of triethanolamine oxide
Example 3
Referring to example 1, the volume ratio of isopropanol to n-hexane as precipitant was changed, and the other conditions were unchanged, and triethanolamine oxide was separated and recovered from the fullerene derivative-containing system. The specific results are shown in Table 2. As can be seen, the recovery rate and purity of the triethanolamine oxide are highest when the volume ratio of isopropanol to n-hexane is 7:5, and the recovery rate can reach 87% and the purity can reach 95%, so that the solvent with the ratio is preferably used as a precipitator.
TABLE 2 influence of different isopropanol and n-hexane volume ratios on recovery of triethanolamine oxide
Example 4
Referring to example 1, the composition and the volume ratio of the precipitant were changed, and the triethanolamine oxide was separated and recovered from the fullerene derivative-containing system under the same conditions. The specific results are shown in Table 3: it can be seen that the recovery of triethanolamine oxide is highest when the volume ratio of isopropanol, n-hexane and anhydrous diethyl ether is 7:5:0, and the recovery can reach 87%, so that solvents in this ratio are preferred as precipitants.
TABLE 3 influence of different volume ratios of isopropanol, n-hexane, and dehydrated ether on recovery of triethanolamine oxide
Example 5
Referring to example 1, the triethanolamine oxide was changed: fullerene: the mole ratio of the chromium trioxide is unchanged, and other conditions are unchanged, and the triethanolamine oxide is separated and recovered in a fullerene derivative-containing system. The specific results are shown in Table 4: therefore, the recovery rate of the final triethanolamine can reach more than 80%, and the purity of the recovered triethanolamine is more than 90%.
Table 4 different triethanolamine oxides: fullerene: effect of chromium trioxide molar ratio on recovery of triethanolamine oxide
Comparative example 1
Several other amine oxide materials reported previously, and the corresponding purification procedures and results are shown in table 5.
Table 5 presents reported purification methods and results for other amine oxide materials
[1] Ding Yuqiu Synthesis and Performance research of amine oxide type surfactants containing dehydroabietyl group [ D ]. University of Guangxi nationality, 2014.
[2] Shang Xuejun, zhang Zhuyong Synthesis and Properties of sulfoamine oxide-containing surfactants [ J ]. Proc. Huadong chemical society, 1992 (02): 227-232.
[3] Zhao Xinlin investigation of the reactive emulsion polymerization System of tertiary amine oxides [ D ]. University of great company, 2014.
Compared with other purification methods of amine oxide in Table 6, the method for purifying the triethanolamine oxide is simple, and the recovery rate and the purity of the recovered triethanolamine oxide are higher.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A method for producing fullerene water-soluble derivatives and recovering triethanolamine oxide is characterized in that the triethanolamine oxide is mixed with fullerene and chromium trioxide according to a certain proportion, then carbon tetrachloride solution is added for mixing reaction, water is added after the reaction is finished, the mixture is stirred and then is kept stand for the first time, and an upper layer of water layer is separated and taken; adding a precipitant into the obtained water layer, wherein oily liquid appears at the bottom of the solution, standing for the second time, separating liquid, taking a lower-layer oil phase, adding water into the taken oil phase for dissolution, adding a carbon tetrachloride solution, standing for the third time, separating liquid, drying the uppermost-layer oil layer to obtain the recovered triethanolamine oxide, and obtaining the fullerene water-soluble derivative as the bottom layer, wherein the precipitant is one or more of isopropanol and n-hexane.
2. The method of claim 1, wherein the triethanolamine is an amine oxide: fullerene: chromium trioxide molar ratio = 50-150:1:10-30.
3. The method according to claim 1, wherein when two mixtures are selected as precipitants, the volume ratio of isopropanol to n-hexane is 3:5 to 9:5.
4. A method according to claim 3, characterized in that when two mixtures are selected as precipitants, the volume ratio of isopropanol to n-hexane is 7:5 to 9:5.
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