CN112920154B - Method for catalyzing synthesis of vitamin E acetate by doping polyaniline with sodium bisulfate - Google Patents
Method for catalyzing synthesis of vitamin E acetate by doping polyaniline with sodium bisulfate Download PDFInfo
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Abstract
The invention discloses a method for synthesizing vitamin E acetate by sodium bisulfate doped polyaniline catalysis, which comprises the following steps: s1: preparing polyaniline: s2: preparing sodium bisulfate doped polyaniline: mixing polyaniline obtained in the step S1 with sodium bisulfate according to the weight ratio of 1: adding the mixture into 20mL of absolute ethyl alcohol according to the mass ratio of 1, stirring and dissolving, re-condensing and refluxing for 4-5 h, decompressing and filtering, and drying at 90 ℃ to constant weight; s3: catalytic synthesis of vitamin E acetate: acetic anhydride and vitamin E are mixed according to the proportion of (1.2-2.0): 1, adding sodium bisulfate doped polyaniline accounting for 0.4-1.2 percent of the total mass of the reactants, carrying out esterification reaction for 30-110 min under the reflux condition of 45-65 ℃, removing sodium bisulfate doped polyaniline by suction filtration, and removing residual acetic anhydride by vacuum distillation of filtrate. The sodium bisulfate doped polyaniline has higher solvent stability, more stable chemical property, easy separation and recovery, repeated use, environmental protection and reduced production cost; at the same time, PAn-NaHSO 4 The catalyst is in an amorphous state and has high catalytic activity.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for catalyzing vitamin E acetate by doping polyaniline with sodium bisulfate.
Background
The natural vitamin E is also called tocopherol, which is mainly obtained by molecular distillation and extraction from fatty acid distillate, the purity is about 50%, and then the purity can be improved to more than 90% by adsorption and other methods. The high-purity natural vitamin E is easy to oxidize and deteriorate and is not easy to preserve, but can be preserved by a microcapsule technology and esterification into corresponding ester derivatives. The natural vitamin E acetate is prepared by esterifying natural vitamin E with acetic anhydride, is vitamin E derivative, is more stable than unesterified natural vitamin E, is easily dissolved in organic solvent, is miscible with acetone, chloroform, diethyl ether and vegetable oil, and is light yellow or colorless transparent viscous oily liquid at room temperature; meanwhile, the vitamin E acetate has wide application and important application in the fields of food and feed additives, cosmetics, medicines, chemical industry and the like. Thus, synthesis of vitamin E acetate is also one of the research hotspots in the chemical industry.
Sodium bisulfate is used as a catalyst, has low price, can catalyze organic synthesis, and has good effect particularly in catalyzing condensation and dehydration reactions. Sodium bisulfate is used as a catalyst, and in the catalytic synthesis reaction process, the reaction condition is mild, the yield is high, and the post-treatment process is simple. When sodium bisulfate is used as a catalyst to catalyze the synthesis of organic matters, dehydration reaction occurs among molecules of the organic matters. Sodium bisulfate is used for catalyzing the dehydration reaction of organic matters to be mainly divided into: the reaction for synthesizing ether, the reaction for synthesizing acetal (ketal), the reaction for synthesizing oxygen-containing hybridization, the nitration reaction and the esterification reaction. In the reaction of synthesizing ether, lin Dejuan and the like are catalyzed and synthesized by sodium bisulfate, chen Xiantao and the like are synthesized into 2-ethoxynaphthalene by sodium bisulfate; in the reaction of synthesizing acetal (ketal), cui Jianlan and the like are catalyzed and synthesized into heptanal diethyl acetal by sodium bisulfate, shanxin and the like are catalyzed and synthesized into cyclohexanone diethyl acetal by sodium bisulfate, liu Yu and the like are catalyzed and synthesized into vanillin propylene glycol acetal by sodium bisulfate; in the synthesis of the oxygen-containing hybrid reaction, liu Di and the like are catalyzed and synthesized into the oxygen-containing xanthene compound by sodium bisulfate; in the nitration reaction, liu Lirong and the like studied the nitration reaction of toluene under the catalysis of sodium bisulfate; in the esterification reaction, sodium bisulfate is used as a catalyst for synthesizing aspirin, sodium bisulfate is used for catalyzing and synthesizing isopropyl acetate for Xu Changlong, sodium bisulfate is used for catalyzing and synthesizing isoamyl chloroacetate for Li Gugui, and sodium bisulfate is used for catalyzing and synthesizing cyclohexyl cinnamate for Gao Yanping.
Sodium bisulfate is directly used as an organic matter synthesis catalyst, and is insoluble in organic esters but not easy to recycle, can be used as waste liquid to be dumped, has certain pollution to the environment, increases the production cost and cannot be recycled. Therefore, how to develop a novel environment-friendly catalyst capable of recycling by utilizing sodium bisulfate, and apply the novel environment-friendly catalyst to the catalytic synthesis of vitamin E acetate, so as to solve the technical problems of production cost and realization of industrial batch production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for synthesizing vitamin E acetate by doping polyaniline with sodium bisulfate.
The technical scheme of the invention is summarized as follows:
a method for synthesizing vitamin E acetate by sodium bisulfate doped polyaniline catalysis comprises the following steps:
s1: preparing polyaniline:
a. dissolving 0.04mol of ammonium persulfate in 20mL of 0.01mol/L HCl solution to obtain ammonium persulfate-HCl mixed solution;
b. adding 0.03mol of aniline into 10mL of 0.01mol/L HCl solution, and magnetically stirring for 20min to obtain an aniline-HCl mixed solution;
c. dropwise adding the ammonium persulfate-HCl mixed solution into the aniline-HCl mixed solution while continuously stirring for 30-50 min to obtain a reaction solution;
d. standing for 24 hours after the temperature of the reaction solution is stable, filtering under reduced pressure, washing with deionized water until the pH value of the filtrate is 7.0, and drying at 70 ℃ until the weight is constant to obtain polyaniline;
s2: preparing sodium bisulfate doped polyaniline: mixing polyaniline obtained in the step S1 with sodium bisulfate according to the weight ratio of 1: adding the mixture into 20mL of absolute ethyl alcohol according to the mass ratio of 1, stirring and dissolving, re-condensing and refluxing for 4-5 h, decompressing and filtering, and drying at 90 ℃ to constant weight to obtain sodium bisulfate doped polyaniline;
s3: catalytic synthesis of vitamin E acetate: acetic anhydride and vitamin E are mixed according to the proportion of (1.2-2.0): 1, adding sodium bisulfate doped polyaniline accounting for 0.4-1.2% of the total mass of reactants, carrying out esterification reaction for 30-110 min under the reflux condition of 45-65 ℃, removing sodium bisulfate doped polyaniline by suction filtration, and removing residual acetic anhydride by vacuum distillation of filtrate to obtain vitamin E acetate.
Preferably, in S3, acetic anhydride and vitamin E are mixed in the following proportions (1.2 to 1.6): 1, adding sodium bisulfate doped polyaniline accounting for 0.6 to 1.0 percent of the total mass of the reactants, and carrying out esterification reaction for 50 to 90 minutes under the reflux condition of 50 to 60 ℃.
Preferably, in S3, acetic anhydride and vitamin E are mixed in an amount of 1.4:1, adding sodium bisulfate doped polyaniline accounting for 1.0 percent of the total mass of the reactants, and carrying out esterification reaction for 50 minutes under the reflux condition of 55 ℃.
The invention has the beneficial effects that:
1. the invention firstly utilizes sodium bisulfate doped polyaniline as a catalyst for synthesizing vitamin E acetate, and obviously improves the yield of the vitamin E acetate, and the yield of the vitamin E acetate reaches 96.60 percent under the conditions that the molar ratio of acetic anhydride to vitamin E is 1:1.4, the reaction temperature is 55 ℃, the reaction time of 50min and the catalyst dosage are 1.0 percent of the total mass of reactants.
2. According to the invention, the sodium bisulfate doped polyaniline is used as the catalyst, and the polyaniline is insoluble in common solvents and is not easy to absorb water and wet, so that the sodium bisulfate in the sodium bisulfate doped polyaniline has higher solvent stability, stable chemical property, easy separation and recovery and repeated use, environmental pollution reduction and environmental protection, and production cost reduction; at the same time, PAn-NaHSO 4 In an amorphous state, increase the simple substance NaHSO 4 And the specific surface area of the catalyst is improved.
Drawings
FIG. 1 is a flow chart of a method for synthesizing vitamin E acetate by sodium bisulfate-doped polyaniline catalysis in the invention;
FIG. 2 is an XRD pattern for polyaniline produced in accordance with an embodiment of the present invention;
FIG. 3 shows sodium bisulfate-doped polyaniline (PAn-NaHSO) prepared according to an embodiment of the present invention 4 ) XRD pattern;
FIG. 4 is an XRD pattern of PAn-NaHSO4 of the present invention after 5 repeated uses.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
The invention provides a method for synthesizing vitamin E acetate by sodium bisulfate doped polyaniline, which comprises the following steps:
s1: preparing polyaniline:
a. dissolving 0.04mol of ammonium persulfate in 20mL of 0.01mol/L HCl solution to obtain ammonium persulfate-HCl mixed solution;
b. adding 0.03mol of aniline into 10mL of 0.01mol/L HCl solution, and magnetically stirring for 20min to obtain an aniline-HCl mixed solution;
c. dropwise adding the ammonium persulfate-HCl mixed solution into the aniline-HCl mixed solution while continuously stirring for 30-50 min to obtain a reaction solution;
d. standing for 24 hours after the temperature of the reaction solution is stable, filtering under reduced pressure, washing with deionized water until the pH value of the filtrate is 7.0, and drying at 70 ℃ until the weight is constant to obtain polyaniline;
s2: preparing sodium bisulfate doped polyaniline: mixing polyaniline obtained in the step S1 with sodium bisulfate according to the weight ratio of 1: adding the mixture into 20mL of absolute ethyl alcohol according to the mass ratio of 1, stirring and dissolving, re-condensing and refluxing for 4-5 h, decompressing and filtering, and drying at 90 ℃ to constant weight to obtain sodium bisulfate doped polyaniline;
s3: catalytic synthesis of vitamin E acetate: acetic anhydride and vitamin E are mixed according to the proportion of (1.2-2.0): 1, adding sodium bisulfate doped polyaniline accounting for 0.4-1.2% of the total mass of reactants, carrying out esterification reaction for 30-110 min under the reflux condition of 45-65 ℃, removing sodium bisulfate doped polyaniline by suction filtration, removing residual acetic anhydride by reduced pressure distillation of filtrate, further analyzing and measuring by an Abbe refractometer, measuring the refractive index of the product to be 1.4957 +/-0.0002, and determining that the product is vitamin E acetate and is light yellow transparent viscous liquid.
The polyaniline and sodium bisulfate-doped polyaniline required in the following examples were prepared as follows:
(1) Preparing polyaniline:
a. dissolving 0.04mol of ammonium persulfate in 20mL of 0.01mol/L HCl solution to obtain ammonium persulfate-HCl mixed solution;
b. adding 0.03mol of aniline into 10mL of 0.01mol/L HCl solution, and magnetically stirring for 20min to obtain an aniline-HCl mixed solution;
c. dropwise adding the ammonium persulfate-HCl mixed solution into the aniline-HCl mixed solution while continuously stirring for 30min to obtain a reaction solution;
d. standing for 24h after the temperature of the reaction solution is stable, filtering under reduced pressure, washing with deionized water until the pH value of the filtrate is 7.0, and drying at 70 ℃ until the weight is constant to obtain polyaniline (PAn);
(2) Preparing sodium bisulfate doped polyaniline: weighing 2.0g polyaniline and 2.0g sodium bisulfate, adding into 20mL absolute ethanol, stirring for dissolving, re-condensing and refluxing for 5h, filtering under reduced pressure, and drying at 90deg.C to constant weight to obtain sodium bisulfate doped polyaniline (PAn-NaHSO) 4 )。
Para-polyaniline and prepared catalyst PAn-NaHSO 4 Characterization was performed
Weighing 0.1g of polyaniline and 0.1g of catalyst PAn-NaHSO prepared by the method 4 Sample, grinding the two into powder respectively, drying, testing with X-ray diffractometer under 30KV and 20mA conditions, polyaniline and catalyst PAn-NaHSO 4 The XRD patterns of (a) are shown in fig. 2 and 3, respectively.
As shown in fig. 2, when the intensity of the peak starts to increase from 5 ° to about 20 °, the peak reaches a maximum value, the peak starts to decrease rapidly after passing 20 ° and the gradient of the peak decrease becomes relatively gentle after passing 30 °, and the substance is determined to be polyaniline by referring to the polyaniline pattern.
As shown in fig. 3, a small peak is present in the interval of 13 ° to 15 °, and a peak is present in the interval of 20 ° to 25 °, which indicates that the large blunt peak of the doped polyaniline is disappeared in the interval of about 20 °, the fall is relatively rapid in the interval of 25 ° to 30 °, and the fall is relatively gentle after 30 °, unlike fig. 2, which indicates that sodium bisulfate is doped into the polyaniline carrier.
Examples 1 to 5 study of the effect of the molar ratio of acetic anhydride to vitamin E on the yield of esters
The molar ratio of acetic anhydride to vitamin E in examples 1 to 5 was 1.2: 1. 1.4:1. 1.6: 1. 1.8: 1. 2.0:1, a step of; the method specifically comprises the following steps:
s1, a strategy is adopted; s2, a strategy is adopted;
s3: catalytic synthesis of vitamin E acetate: acetic anhydride and vitamin E are mixed according to the proportion of (1.2-2.0): 1, adding sodium bisulfate doped polyaniline accounting for 0.6 percent of the total mass of reactants, carrying out esterification reaction for 50 minutes under the reflux condition of 60 ℃, filtering to remove sodium bisulfate doped polyaniline, and distilling the filtrate under reduced pressure to remove residual acetic anhydride to obtain the vitamin E acetate.
Table 1 shows the effect of the molar ratio of acetic anhydride to vitamin E on the yield of esters
Table 1:
as shown in Table 1, as the amount of acetic anhydride was increased, the yield of the product was gradually increased, and when the molar ratio of acetic anhydride to vitamin E was 1.4:l, the yield reached 86.62%, after which the amount of acetic anhydride was increased continuously, and the esterification rate was not increased, but rather tended to decrease. Since vitamin E is easily oxidized, the esterification rate is low when the molar ratio of acetic anhydride to vitamin E is less than 1.4:1, and at this time, a proper excess of acetic anhydride increases the reaction yield, and when the amount of acetic anhydride reaches a certain level, the contact of the reaction molecules is hindered, thereby decreasing the esterification rate. Thus the optimal molar ratio of acetic anhydride to vitamin E is 1.4:1.
Examples 6 to 10 study of the influence of the reaction temperature on the yield of esters
Examples 6 to 10 use acetic anhydride and vitamin E in a molar ratio of 1.4:1, PAn-NaHSO 4 The amount of the catalyst is 0.6% of the total mass of the reactants, the reaction temperature is 50min, and the difference is that: the reaction temperatures of examples 6 to 10 were 45℃and 50℃and 55℃and 60℃and 65℃in this order. As shown in table 2:
table 3 shows the results of the reaction temperature on the yield of esters
Table 3:
as can be seen from Table 3, the reaction temperature has a great influence on the esterification rate, the esterification rate increases with the temperature rise, the esterification rate is maximum at 55 ℃, the temperature is higher, and the yield is reduced; because the higher the temperature is, the larger the average kinetic energy of the reactant molecules is, and other side reactions are increased in the reaction when the temperature is too high, so that the esterification rate is reduced. Thus 55℃is the optimal reaction temperature.
Examples 11 to 15 study the influence of the reaction time on the yield of esters
Examples 11 to 15 use acetic anhydride and vitamin E in a molar ratio of 1.4:1, and the reaction temperature was 55deg.C, PAn-NaHSO 4 The amount of (2) is 0.6% of the total mass of the reactants, the difference is that: the reaction times of examples 6 to 10 were 30min, 50min, 70min, 90min, 110min in this order. As shown in table 4:
table 4:
table 5 shows the results of the reaction time on the yield of esters
Table 5:
as shown in Table 5, the esterification rate was high at 50min, and after more than 50min, the yield was gradually decreased with the increase of the reaction time, so that the reaction time was reasonable at 50min. Because the esterification and the hydrolysis are synchronously carried out in the reaction, the esterification rate is not improved after the balance, and the hydrolysis of vitamin E acetate can be caused by the continuous heating, so that the ester yield is reduced. The optimal reaction time is 50min.
Examples 16 to 20 study the effect of catalyst usage on the yield of esters
The molar ratio of acetic anhydride to vitamin E is 1.4:1, the reaction temperature is 55 ℃, the reaction time is 50min, and the difference is that: the PAn-NaHSO4 used in examples 6 to 10 was 0.4%, 0.6%, 0.8%, 1.0% and 2.0% by weight of the total mass of the reactants. As shown in table 6:
table 6:
table 7 shows the results of the effect of catalyst amount on the yield of esters
Table 7:
as is clear from Table 7, when the catalyst amount is small, the catalytic effect is poor and the vitamin E acetate yield is not high. The yield increases gradually with increasing catalyst usage. When the catalyst dosage is 1.0%, the yield reaches the highest; the product yield decreases when the catalyst amount is increased, which indicates that the catalyst amount is not as high as possible, but the product yield is highest at 1.0%.
EXAMPLES 16 TO 20 EXAMPLES catalyst PAn-NaHSO 4 Influence of the number of repeated uses on the yield of esters
Examples 16 to 20 the molar ratio of acetic anhydride to vitamin E was 1.4:1, the amount of PAn-NaHSO4 was 1.0%, the reaction temperature was 55deg.C, and the reaction time was 50min, the difference was: PAn-NaHSO in examples 16 to 20 4 The repeated use times are 1, 2, 3, 4 and 5 times in turn.
Table 8 shows PAn-NaHSO 4 Effect of number of repeated use on ester yield results:
table 8:
from fig. 8, it was found that the yield of vitamin E acetate was 93.47% after 5 times of catalyst use and the yield of the first time use were slightly different, and thus it was found that the number of times of catalyst reuse had a weak effect on the yield of the product.
PAn-NaHSO after 5 times of repeated use in example 20 4 The catalyst was ground to a powder, dried and tested with an X-ray diffractometer at 30KV,20 mA. The XRD patterns are shown in FIG. 4: a small peak in the 13 deg. to 14 deg., a peak in the 20 deg. to 26 deg., a relatively rapid drop in the 25 deg. to 30 deg. interval, and a relatively gentle drop after 30 deg., similar to the XRD pattern of FIG. 3, showing the catalyst PAn-NaHSO 4 The structure and chemical properties of the PAn-NaHSO are not changed, which indicates that the PAn-NaHSO of the invention 4 The chemical nature of the catalyst is relatively stable.
Orthogonal test results and analysis
The orthometric test of 4 factor 3 level was designed with the molar ratio of acetic anhydride to vitamin E set to (A), the reaction temperature (B), the reaction time (C) and the catalyst amount (D), and the results are shown in Table 9.
TABLE 9 orthogonal test design and results
According to the numerical values of the table 9,R, the maximum effect is the maximum, that is, the effect of the reaction temperature on the reaction is the maximum, the effect of the reaction time on the reaction is smaller, and the order of the influencing factors is B>A>D>C, the optimal reaction condition can be determined to be A according to R and k 2 B 2 C 1 D 3 Namely, when the molar ratio of acetic anhydride to vitamin E is 1:1.4, the reaction temperature is 55 ℃, the reaction time is 50min, and the catalyst dosage is 1.0% of the total mass of reactants, the reaction effect is best, and the yield of vitamin E acetate is higher.
Verification test
At A 2 B 2 C 1 D 3 Under the optimal experimental conditions, the vitamin E acetate yield is 96.59% and 96.61% respectively after 2 times of parallel experiments, and the average yield is 96.60%, which shows that the conditions obtained by the orthogonal experiment are more standard and the stability of repeated experiments is better.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (3)
1. The synthesis method for catalyzing vitamin E acetate by sodium bisulfate doped polyaniline is characterized by comprising the following steps of:
s1: preparing polyaniline:
a. dissolving 0.04mol of ammonium persulfate in 20mL of 0.01mol/L HCl solution to obtain ammonium persulfate-HCl mixed solution;
b. adding 0.03mol of aniline into 10mL of 0.01mol/L HCl solution, and magnetically stirring for 20min to obtain an aniline-HCl mixed solution;
c. dropwise adding the ammonium persulfate-HCl mixed solution into the aniline-HCl mixed solution while continuously stirring for 30-50 min to obtain a reaction solution;
d. standing for 24 hours after the temperature of the reaction solution is stable, filtering under reduced pressure, washing with deionized water until the pH value of the filtrate is 7.0, and drying at 70 ℃ until the weight is constant to obtain polyaniline;
s2: preparing sodium bisulfate doped polyaniline: mixing polyaniline obtained in the step S1 with sodium bisulfate according to the weight ratio of 1: adding the mixture into 20mL of absolute ethyl alcohol according to the mass ratio of 1, stirring and dissolving, re-condensing and refluxing for 4-5 h, decompressing and filtering, and drying at 90 ℃ to constant weight to obtain sodium bisulfate doped polyaniline;
s3: catalytic synthesis of vitamin E acetate: acetic anhydride and vitamin E are mixed according to the proportion of (1.2-2.0): 1, adding sodium bisulfate doped polyaniline accounting for 0.4-1.2% of the total mass of reactants, carrying out esterification reaction for 30-110 min under the reflux condition of 45-65 ℃, removing sodium bisulfate doped polyaniline by suction filtration, and removing residual acetic anhydride by vacuum distillation of filtrate to obtain vitamin E acetate.
2. The method for synthesizing vitamin E acetate by sodium bisulfate-doped polyaniline catalysis according to claim 1, wherein in S3, acetic anhydride and vitamin E are mixed according to the following ratio (1.2-1.6): 1, adding sodium bisulfate doped polyaniline accounting for 0.6 to 1.0 percent of the total mass of the reactants, and carrying out esterification reaction for 50 to 90 minutes under the reflux condition of 50 to 60 ℃.
3. The method for synthesizing vitamin E acetate by sodium bisulfate-doped polyaniline catalysis according to claim 2, wherein in S3, acetic anhydride and vitamin E are mixed according to a ratio of 1.4:1, adding sodium bisulfate doped polyaniline accounting for 1.0 percent of the total mass of the reactants, and carrying out esterification reaction for 50 minutes under the reflux condition of 55 ℃.
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