CN111848569B - Synthetic method of acetic acid glycerol ketal ester - Google Patents
Synthetic method of acetic acid glycerol ketal ester Download PDFInfo
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- CN111848569B CN111848569B CN202010813272.9A CN202010813272A CN111848569B CN 111848569 B CN111848569 B CN 111848569B CN 202010813272 A CN202010813272 A CN 202010813272A CN 111848569 B CN111848569 B CN 111848569B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
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Abstract
The invention discloses a method for synthesizing glycerol acetate acetonide ester, and relates to the technical field of chemical synthesis. The synthesis method of the acetic acid glycerol ketal ester provided by the invention takes acetic acid and glycerol ketal as raw materials to react at low temperature under the synergistic effect of the catalyst and a Pulsed Electric Field (PEF) to generate the acetic acid glycerol ketal ester, thereby achieving the purpose that the catalyst can achieve higher catalytic efficiency at lower temperature. The synthesis method provided by the invention has the characteristics of low reaction temperature, short reaction time, high efficiency, easily controlled conditions, environmental friendliness, low production cost, suitability for industrial mass production and the like.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthetic method of acetic acid glycerol ketal ester.
Background
Glycerol acetate acetonide is an organic compound with a bifunctional structure, and the chemical structure of the glycerol acetate acetonide is as follows:
the acetin molecules contain ether bonds, ester bonds and different alkyl groups, and based on the principle of similarity and intermiscibility, the acetin molecules can dissolve organic molecules and synthesize natural high molecular compounds and can be mutually dissolved with water or water-soluble compounds to different degrees. The solvent performance is superior to that of common solvents (such as ethyl acetate, acetone, xylene, and the like), small molecular organic matters, large molecular organic matters, synthetic and natural high molecular organic matters can be dissolved, and an azeotrope can be formed with water. Its performance is superior to glycol ether and propylene glycol ether, and it has very strong dissolving power, especially for polymer. It can improve the performance of paint and ink, reduce filming temperature, increase luster, raise the adhesion, insulating property and fastness of paint film. Therefore, it has properties which are not possessed by general organic solvents.
The synthesis method of the acetic acid glycerol acetonide is wide, and can be catalyzed and synthesized by catalysts such as sulfonic acid catalysts, molecular sieve catalysts, heteropoly acid catalysts, solid super acidic catalysts, bisulfate catalysts, ionic liquid catalysts, ion exchange resin catalysts and the like, and the synthesis methods are different in thousands of autumn.
Ion exchange resins are insoluble, high molecular weight compounds, usually spherical particles, with functional groups (active groups that exchange ions) and a network structure. In solution it can exchange its own ions with the same number of ions in solution. The ion exchange resin catalyst has the advantage of easy separation from the product and also has better catalytic activity for esterification reaction. But the application is limited due to the low use temperature.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome some defects in the background technology and provide a synthetic method of acetic glycerol ketal ester, which has high catalytic efficiency, can react at low temperature and has low production cost.
In order to solve the above problems, the present invention proposes the following technical solutions:
a synthesis method of acetic acid glycerol acetonide ester comprises reacting acetic acid and glycerol acetonide at a molar ratio of 1:1-6 under pulsed electric field, wherein the amount of catalyst is 0.001-1% of the total mass of reactants.
The reaction formula of the synthesis method of the acetic acid glycerol ketal ester provided by the invention is as follows:
the further technical proposal is that the molar ratio of acetic acid and glycerol acetonide is 1: 2-5.
The further technical proposal is that the reaction temperature is 20-70 ℃.
The further technical proposal is that the reaction temperature is 20-60 ℃.
The technical scheme is that the electric field intensity of the pulse electric field is 0-30.0 k V/cm.
The further technical proposal is that the pulse frequency of the pulse electric field is 0.8-1.2k Hz.
The further technical proposal is that the pulse width of the pulse electric field is 25.0-35 mus.
The further technical scheme is that the catalyst is an ion exchange resin catalyst.
The technical scheme is that the catalyst is any one of Amberlyst-15 resin, NKC-9 resin, D001cc resin, D72 resin and 732 resin.
The further technical scheme is that the catalyst needs to be pretreated before use, and the pretreatment process is as follows:
soaking the resin in absolute ethyl alcohol with the volume 1.5-3 times that of the resin for 3-5 h;
washing with deionized water, and activating the resin;
washing the resin with deionized water after the activation is finished until the pH of the washing liquid is the same as that of the deionized water;
drying the resin in an oven at 80 ℃ after drying the resin in the air at 30-50 ℃.
The pulse electric field is generated by a pulse electric field continuous processing system; the pulse electric field continuous processing system comprises an oscilloscope, a load resistor, a pulse generator, a processing chamber and a constant flow pump; the oscilloscope is connected with the load resistor and the pulse generator in series, and the pulse generator is arranged in the processing chamber; the constant flow pump is respectively communicated with the reaction liquid storage tank and the processing chamber, and conveys reactants in the reaction liquid storage tank to the processing chamber.
The treatment chamber is provided with an electrode made of stainless steel. In the processing chamber, the insulating material is polytetrafluoroethylene.
The volume of the chamber was 0.0212mL and the pulse waveform was a square flat wave.
In the present invention, the pulsed electric field has a great effect of promoting the esterification reaction, and the use of the pulsed electric field does not increase the concentration of the reactant and does not increase the reaction temperature. The pulse electric field influences the esterification reaction mechanism of the alcohol acid water-containing system. Mainly comprises two aspects, one is that the pulsed electric field promotes the weak electrolyte acetic acid to ionize more H+The formation of a tetrahedral active intermediate in the esterification reaction process is accelerated, the activation energy of the esterification reaction is reduced, and the reaction rate is increased; on the other hand, the pulse electric field destroys hydrated ions and hydrated molecular structures in the system, more free ions and molecules are exposed outside, and the collision probability among reactant molecules is increased, so that the reaction rate is increased.
Compared with the prior art, the invention can achieve the following technical effects:
the synthesis method of the acetic acid glycerol ketal ester provided by the invention takes acetic acid and glycerol ketal as raw materials to react at low temperature under the synergistic effect of the catalyst and a Pulsed Electric Field (PEF) to generate the acetic acid glycerol ketal ester, thereby achieving the purpose that the catalyst can achieve higher catalytic efficiency at lower temperature. The pulse electric field is used together with a catalyst only by applying an external electric field without increasing the concentration of reactants or raising the temperature, so that the catalytic efficiency is further improved, the reaction time is shortened, and the pulse electric field has a synergistic effect.
The synthesis method provided by the invention has the characteristics of low reaction temperature, short reaction time, high efficiency, easily controlled conditions, environmental friendliness, lower production cost, suitability for industrial mass production and the like.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The synthesis method of the acetic glycerol ketal ester provided by the embodiment of the invention takes acetic acid and glycerol ketal as raw materials to react at low temperature under the synergistic effect of ion exchange resin and Pulsed Electric Field (PEF) to generate the acetic glycerol ketal ester.
The reaction formula of the synthesis method of the acetic acid glycerol ketal ester provided by the invention is as follows:
in other embodiments, the ion exchange resin catalyst is pretreated prior to use, the pretreatment process comprising: soaking the resin in absolute ethyl alcohol with the volume twice that of the resin for 4 hours to remove impurities and pigments in the resin; then washing with deionized water, and soaking with 5 times of dilute hydrochloric acid solution with the mass fraction of 5% -6% for 24h to activate the resin; then washing with deionized water until the pH is the same as that of the used deionized water; drying at lower temperature (such as 40 deg.C), and oven drying at 80 deg.C.
The pulse electric field is generated by a pulse electric field continuous processing system; the pulse electric field continuous processing system comprises an oscilloscope, a load resistor, a pulse generator, a processing chamber and a constant flow pump; the oscilloscope is connected with the load resistor and the pulse generator in series, and the pulse generator is arranged in the processing chamber; the constant flow pump is respectively communicated with the reaction liquid storage tank and the processing chamber, and conveys reactants in the reaction liquid storage tank to the processing chamber.
It should be noted that the pulsed electric field continuous processing system may further comprise auxiliary equipment such as a digital thermometer, a rotameter, and a constant temperature circulator, the electrode material of the processing chamber is stainless steel, the insulating part is polytetrafluoroethylene, and the capacity is 0.0212m L. The skilled person can add or design the pulsed electric field continuous processing system according to the need; the person skilled in the art can also purchase the existing pulse generating device to generate the pulse, and as long as the parameters of the pulse electric field are controlled within the specified range of the present invention, the method provided by the present invention operates to obtain the corresponding technical effect, and all that is within the protection scope of the present invention.
In other embodiments, the pulsed electric field parameters are: the electric field intensity is 0-30.0 k V/cm, the pulse frequency is 1.0k Hz, and the pulse width is 30.0 mu s; the waveform is a flat square wave.
The following are specific embodiments:
examples one class (reactions at different PEF field strengths):
the ratio of the alcohol to the acid is 1:2, the reaction temperature is controlled at 50 ℃, the flow rate is constant at 20m L/min, an electric field with the field intensity of 0, 10, 15, 20, 25 and 30.0k V/cm is respectively applied to 0.4 percent Amberlyst-15 resin catalyst for synergistic treatment, and the circulating treatment time is 1.5 h.
Examples are of the second type (reaction at different ratios of alcohol to acid):
the reaction temperature is controlled at 50 ℃, the flow rate is constant at 20m L/min, 0.4 percent Amberlyst-15 resin catalyst is selected to be cooperatively treated with an electric field of 20k V/cm, and the circulating treatment time is 1.5 h. The molar ratio of the sample alcohol acid is 1:1, 1:2, 1:3, 1:4 and 1:5 respectively.
Examples three classes (reaction with different ion exchange resin catalysts):
the ratio of alcoholic acid to acid is 1:2, the reaction temperature is controlled at 50 ℃, the flow rate is constant at 20m L/min, the electric field intensity is 20k V/cm, the ion exchange resin catalysts are Amberlyst-15 resin, D001cc resin and 732 type strong acid cation exchange resin respectively, the dosage is 0.4 percent, a blank group is arranged, and the cycle treatment time is 1.5 h.
Examples are four types (reaction at different amounts of ion exchange resin catalyst):
the ratio of alcohol to acid is 1:2, the reaction temperature is controlled at 50 ℃, the flow rate is constant at 20m L/min, the electric field intensity is 20k V/cm, the ion exchange resin catalyst is Amberlyst-15 resin, the dosage of the catalyst is respectively 0.01 percent, 0.1 percent, 0.2 percent, 0.4 percent, 0.8 percent and 1 percent of the circulating treatment time is 1.5 h.
Examples five types (reaction at different reaction temperatures)
The ratio of alcohol to acid is 1:2, the reaction temperature is controlled at 40 ℃, the flow rate is constant at 20m L/min, the electric field strength is 20k V/cm, 0.4 percent of Amberlyst-15 ion exchange resin catalyst is used, the reaction temperature is respectively 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, and the cycle treatment time is 1.5 h.
The data for the above example are shown in table 1 below:
table 1: data of each embodiment
As can be seen from the data in Table 1, the yield of the glycerol acetonide acetate provided by the examples of the present invention increased with the increase of the field strength of PEF under otherwise constant conditions. Combining other factors, the reaction conditions are more appropriate: the ratio of glycerol acetonide to acetic acid is 1: 2; the ion exchange resin catalyst is Amberlyst-15 resin; the catalyst dosage is 0.4%; the reaction temperature was 40 ℃.
It should be noted that, by using the method for synthesizing glycerol acetonide acetate provided by the embodiment of the present invention, a yield of 91.9% can be achieved at 30 ℃, and thus, the method for synthesizing glycerol acetonide acetate provided by the present invention has the advantages of mild reaction conditions, high yield, and considering the factors of energy cost, catalyst life, etc., the reaction temperature is preferably 40 ℃.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A synthesis method of acetic acid glycerol acetonide ester is characterized in that acetic acid and glycerol acetonide react under a pulse electric field according to a molar ratio of 1:1-6, and the dosage of a catalyst is 0.001-1% of the total mass of reactants;
the catalyst is any one of Amberlyst-15 resin, NKC-9 resin, D001cc resin, D72 resin and 732 resin;
the electric field intensity of the pulse electric field is 10-30.0 k V/cm;
the pulse frequency of the pulse electric field is 0.8-1.2k Hz;
the pulse width of the pulse electric field is 25.0-35 mus.
2. The method of claim 1, wherein the molar ratio of acetic acid to glycerol acetonide is 1: 2-5.
3. The method of synthesizing glycerol acetonide acetate of claim 1, wherein the reaction temperature is 20-70 ℃.
4. The method of synthesizing glycerol ketal acetate of claim 3, wherein the reaction temperature is 20 to 60 ℃.
5. The method of claim 1, wherein the catalyst is pre-treated before use, and the pre-treatment process comprises the following steps:
soaking the resin in absolute ethyl alcohol with the volume 1.5-3 times that of the resin for 3-5 h;
washing with deionized water, and activating the resin;
washing the resin with deionized water after the activation is finished until the pH of the washing liquid is the same as that of the deionized water;
drying the resin in an oven at 80 ℃ after drying the resin in the air at 30-50 ℃.
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Citations (2)
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| CN103834477A (en) * | 2014-03-14 | 2014-06-04 | 河南久大实业有限公司 | Production method of glycerin fuel |
| CN110526894A (en) * | 2019-08-31 | 2019-12-03 | 浙江工业大学 | A method of solketal acetate is synthesized by glycerol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834477A (en) * | 2014-03-14 | 2014-06-04 | 河南久大实业有限公司 | Production method of glycerin fuel |
| CN110526894A (en) * | 2019-08-31 | 2019-12-03 | 浙江工业大学 | A method of solketal acetate is synthesized by glycerol |
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| Green Acetylation of Solketal and Glycerol Formal by Heterogeneous Acid Catalysts to Form a Biodiesel Fuel Additive;Jennifer R. Dodson等;《ChemSusChem》;20140708;第7卷(第9期);第2728-2734页，尤其是第2729页左栏，scheme1，Figure 1，第2729页Figure 1的上方 * |
| High-Temperature Batch and Continuous-Flow Transesterification of Alkyl and Enol Esters with Glycerol and Its Acetal Derivatives;Calmanti, Roberto等;《Sustainable Chem. Eng.》;20180331;第6卷(第3期);第3964-3973页 * |
| New Class of Acetal Derived from Glycerin as a Biodiesel Fuel Component;Eva Garcı´a等;《Energy & Fuels》;20081231;第22卷(第6期);第4274-4280页 * |
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| On the exergetic optimization of solketalacetin synthesis as a green fuel additive through ketalization of glycerol-derived monoacetin with acetone;Aghbashlo, Mortaza等;《RENEWABLE ENERGY》;20181031;第126卷;第242-253 页 * |
| Synthesis and Characterization of New Solketal Alkylesters Usable as Diesel Biobased Fuel Additives;CONSTANTIN NEAMTU等;《REVISTA DE CHIMIE》;20190430;第70卷(第4期);第1167-1172页 * |
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