CN113788775B - Sulfonic acid functionalized pyrrolidone ionic liquid catalyst, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a sulfonic acid functionalized pyrrolidone ionic liquid catalyst and a preparation method and application thereof. The invention mainly solves the technical problem of preparing sulfonic acid functionalized pyrrolidone ionic liquid in the prior art. The invention heats the pyrrolidone and the alkyl sulfonic acid at 40-330 ℃ by a two-step synthesis method; and adding acid into the previous step, fully reacting at 30-350 ℃, and purifying to obtain a target product. The sulfonic acid functionalized pyrrolidone ionic liquid catalyst comprises pyrrolidone, alkyl sulfonic acid and acid radical ions, wherein the pyrrolidone accounts for 35-55% of the total weight in percentage by weight; the alkyl sulfonic acid accounts for 20 to 50 percent of the total weight; acid radical ions account for 1 to 20 percent of the total weight. The ionic liquid catalyst designed by the invention is applied to the esterification reaction of acid or anhydride and alcohol, has higher catalytic activity, high stability, high reaction rate and less byproducts, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of liquid catalysts, and particularly relates to a sulfonic acid functionalized pyrrolidone ionic liquid catalyst, and a preparation method and application thereof.
Background
The esterified product can be used as an important chemical intermediate and widely applied to the fields of food additives, plasticizers, spices, medical supplies, coatings and the like. In the field of esterification catalysis today, the commonly used catalysts are mainly inorganic acid catalysts, solid super acids, enzyme catalysts, acidic ion exchange resins, heteropolyacids, and partial metal catalysts, such as titanium-based catalysts and aluminum-based catalysts. The catalysts have certain defects in industrial production and certain obstacles to industrial production. With the continuous requirements of the country on environmental protection and the prospect of sustainable development. Ionic liquid catalysis has been the focus of research in recent years.
According to the principle of esterification reaction, protonic acid can catalyze esterification reaction, and ionic liquid shows stronger acidity and has higher activity in esterification reaction. The ionic liquid is a molten electrolyte which is in a liquid state at room temperature and is formed by combining anions and cations. They are non-volatile, have a wide liquid range and can be designed to be strong. The variety of ionic liquids can increase the designated characteristics of the ionic liquid through the design of anions and cations and the introduction of cation functional groups. The pyrrolidone ionic liquid has strong dissolving capacity, strong designability and strong acidity, and is a better choice for esterification reaction. And the introduction of sulfonic acid functional group into the ionic liquid can make the ionic liquid give consideration to the advantages of solid acid and liquid acid, thereby not only improving the acidity of the ionic liquid, but also increasing the stability of the ionic liquid, improving the recycling rate of the ionic liquid and being beneficial to the industrial production of esterification reaction.
The research on sulfonic acid functionalized pyrrolidone ionic liquid at present mainly focuses on the aspect of alkyl sulfonation of 2-pyrrolidone. Patent CM1880303 synthesizes a pyrrolidone ionic liquid and its application in catalytic esterification reaction. Patent CN108658828 discloses N-alkyl substituted pyrrolidone ionic liquid, which is applied to esterification reaction, and results show that the catalytic activity of the pyrrolidone ionic liquid can completely replace the traditional catalyst. Patent CN101024625 discloses that pyrrolidone sulfonic acid inner salt and acid are used as raw materials to synthesize pyrrolidone sulfonic acid functionalized ionic liquid under the condition of 0-120 ℃. The 1- (3-sulfonic acid group) -propyl-2 pyrrolidone hydrosulfate ionic liquid is synthesized in the application of the ionic liquid to the reaction of n-butyl acetate in the literature (Huangbaohua, wanyanfei, rolling, squaring, peribeibearley, the synthesis of pyrrolidone acidic ionic liquid and the catalytic activity of the ionic liquid to the esterification reaction [ J ]. Catalytic science, 2007 (08): 0743-0748). It can be seen that the introduction of sulfonic acid functional group into pyrrolidone ionic liquid has application prospect in esterification reaction. The sulfonic acid with longer alkyl side chain is introduced into the method, the pyrrolidone sulfonated ionic liquid is directly synthesized through pyrrolidone, alkyl sulfonic acid and acid, and the ionic liquid is applied to various esterification reactions, and shows higher activity and stability.
Disclosure of Invention
Aiming at the defects and difficulties in the prior art, the invention aims to provide a novel method.
The invention is realized by the following technical scheme:
the invention provides a sulfonic acid functionalized pyrrolidone ionic liquid catalyst, which comprises pyrrolidone, alkyl sulfonic acid and acid radical ions, and the structural formula of the catalyst is shown as the formula (I):
in the formula, R is alkyl, N is 4-8, and the pyrrolidone is 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-cyclohexylpyrrolidone or N-octylpyrrolidone; b-is
Acid ions such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid;
the pyrrolidone accounts for 35 to 55 percent of the total weight in percentage by weight; the alkyl sulfonic acid accounts for 20 to 50 percent of the total weight; acid radical ions account for 1 to 20 percent of the total weight.
The pH value of the sulfonic acid functionalized pyrrolidone ionic liquid in the scheme is 1.0-3.5; the conductivity is between 0.35 and 1.4S/m; the viscosity is 400 to 750 mPas.
The second aspect of the invention provides a preparation method of the sulfonic acid functionalized pyrrolidone ionic liquid catalyst, which overcomes the problems of complex synthesis of ionic liquid and single type of ionic liquid in the prior art.
The sulfonic acid functionalized pyrrolidone ionic liquid is prepared by the following steps:
s1: preparing an ionic liquid precursor: dissolving pyrrolidone and alkyl sulfonic acid in a molar ratio of 1: 1.0-2.5 in a solvent A, gradually heating to 40-330 ℃, and stirring for 1-48 h, wherein the ionic liquid precursor is the cation of the ionic liquid.
S2: treating an ionic liquid precursor: washing the ionic liquid cation obtained in the step S1 by using a solvent A at normal temperature, and drying at 50-120 ℃ for 1-24 h.
S3: mixing the ionic liquid precursor treated in the step S2 with
Mixing the acid in the molar ratio of 1 to (1.01-3.2), stirring at 30-350 deg.c for 2-48 hr, and evaporating at 50-100 deg.c for 0.5-2 hr to obtain sulfonated ionic liquid.
The solvent A in the scheme is at least one of ethyl acetate, toluene and diethyl ether. The pyrrolidone is at least one of 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, cyclohexylpyrrolidone and N-octylpyrrolidone. The alkyl sulfonic acid is at least one of 1,4 butane sulfonic acid lactone, pentane sulfonic acid, hexane sulfonic acid, heptane sulfonic acid and octane sulfonic acid.
The acid is at least one of concentrated sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid.
The preferable range of the material ratio is as follows: the mol ratio of the pyrrolidone to the alkyl sulfonic acid is 1 to (1.02-1.8), and the ionic liquid precursor and the alkyl sulfonic acid are mixed
The molar ratio of the acid is 1 to (1.02-2.0).
The reaction temperature in the ionic liquid precursor synthesis in the step S1 is 40-200 ℃, the stirring time is 2-10 h, and the ionic liquid precursor in the step S3
The temperature of the acid reaction is 50-200 ℃, and the stirring time is 2-12 h.
In order to overcome the defects of more byproducts, high price, difficult synthesis, difficult separation and the like of the traditional catalyst in the esterification reaction, the sulfonic acid functionalized pyrrolidone ionic liquid catalyst prepared by the invention can be applied to the synthesis of the esterification reaction, and the synthesis method has the advantages of strong acidity, high stability, high catalytic activity, simple synthesis and the like. The method comprises the following specific steps:
the sulfonic acid functionalized pyrrolidone ionic liquid is used as a catalyst, a substance containing acid anhydride or acid and alcohol is used as a raw material, wherein the molar ratio of the acid anhydride or acid to the alcohol is 1: 1.0-20, the mixture of the acid anhydride or acid and alcohol is contacted with the catalyst, the dosage of the catalyst is 0.00001-40 wt% of the total mass of the acid anhydride or acid and alcohol, the catalyst is contacted and reacted with the catalyst under the reaction conditions that the reaction temperature is 80-240 ℃, the reaction time is 1-10 hours and the reaction pressure is 0.05-5 MPa, and the substance containing ester is generated.
In the above scheme, the acid or acid anhydride is at least one of phthalic anhydride, terephthalic acid, naphthalene dicarboxylic acid and acetic acid. The acid is at least one of methanol, ethanol, ethylene glycol, n-butanol, propylene glycol and isooctyl alcohol. The mol ratio of the acid to the alcohol is preferably 1 to (2.1-10), and the dosage of the ionic liquid is preferably 0.0001-15% of the total mass of the acid and the alcohol.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention synthesizes sulfonic acid functionalized pyrrolidone ionic liquid catalyst by a two-step method, the catalyst contains alkyl sulfonic acid with the mass fraction of 20-50%, and the pH of the ionic liquid catalyst is 1.0-3.5; the conductivity is between 0.35 and 1.4S/m; the viscosity is 400 to 750 mPas.
(2) The preparation method of the sulfonic acid functionalized pyrrolidone ionic liquid catalyst provided by the invention can be used for producing the sulfonated pyrrolidone ionic liquid catalyst, and overcomes the problems of complexity and single type of ionic liquid in the prior art for producing the ionic liquid.
(3) The sulfonic acid functionalized pyrrolidone ionic liquid catalyst and the preparation method thereof can be used in the generation field of esterification reaction, and can improve the conversion rate and selectivity of esterification reaction raw materials and the stability of the catalyst.
Detailed Description
The present invention will be further described with reference to the following examples.
[ example 1 ]
1. Preparing an ionic liquid precursor: dissolving 2-pyrrolidone and hexane sulfonic acid in a molar ratio of 1: 1.5 in ethyl acetate, gradually heating to 50 ℃, stirring for 8h, washing with ethyl acetate after the reaction is finished to remove unreacted materials, and vacuum-drying at 60 ℃ for 4h.
2. Preparation of ionic liquid: mixing the washed ionic liquid precursor and p-toluenesulfonic acid according to the molar ratio of 1: 2.05, stirring at 80 ℃ for 8h, and evaporating at 80 ℃ for 1h after the reaction is finished to obtain yellow viscous liquid.
The obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 45% of pyrrolidone, 50% of hexane sulfonic acid and 5% of p-toluene sulfonic acid group by mass; the ionic liquid catalyst has an electric pH value of 1.5 and an electric conductivity of 0.45S/m; the viscosity was 360 mPas.
[ example 2 ]
1. Preparing an ionic liquid precursor: dissolving N-methylpyrrolidone and hexane sulfonic acid in a molar ratio of 1: 1.1 in solvent toluene, gradually heating to 60 ℃, stirring for 7 hours, washing with toluene after the reaction is finished to remove unreacted materials, and drying in vacuum for 6 hours at 50 ℃.
2. Preparation of ionic liquid: mixing the washed ionic liquid precursor and methanesulfonic acid according to the molar ratio of 1: 1.8, stirring for 8h at 60 ℃, and evaporating for 1h at 60 ℃ after the reaction is finished to obtain yellow viscous liquid.
The obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 35% of pyrrolidone, 55% of hexane sulfonic acid and 10% of methylsulfonic acid by mass; the ionic liquid catalyst has an electric pH value of 1.9 and an electric conductivity of 1.35S/m; the viscosity was 450 mPas.
[ example 3 ]
1. Preparing an ionic liquid precursor: dissolving N-ethyl pyrrolidone and hexane sulfonic acid in a molar ratio of 1: 1.5 in solvent ether, gradually heating to 55 ℃, stirring for 8h, washing with ether after the reaction is finished to remove unreacted materials, and vacuum-drying at 50 ℃ for 6h.
2. Preparation of ionic liquid: mixing the washed ionic liquid precursor and concentrated sulfuric acid in a molar ratio of 1: 1.5, stirring at 80 ℃ for 10h, and evaporating at 80 ℃ for 0.5h after the reaction is finished to obtain yellow viscous liquid.
The obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 37% of pyrrolidone, 55% of hexane sulfonic acid and 8% of hydrogen sulfate by mass fraction; the ionic liquid catalyst has an electric pH value of 1.1 and an electric conductivity of 1.30S/m; the viscosity was 520 mPas.
[ example 4 ]
1. Preparing an ionic liquid precursor: dissolving cyclohexyl pyrrolidone and butane sulfonic acid in a molar ratio of 1: 1.3 in solvent diethyl ether, gradually heating to 90 ℃, stirring for 8h, washing with diethyl ether after the reaction is finished to remove unreacted materials, and drying in vacuum at 50 ℃ for 6h.
2. Preparation of ionic liquid: mixing the washed ionic liquid precursor and p-toluenesulfonic acid according to the molar ratio of 1: 1.3, stirring at 200 ℃ for 38h, and evaporating at 100 ℃ for 0.5h after the reaction is finished to obtain yellow viscous liquid.
The obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 47% of pyrrolidone, 43% of butane sulfonic acid and 10% of p-toluene sulfonate by mass; the ionic liquid catalyst has an electric pH value of 1.8 and an electric conductivity of 0.78S/m; the viscosity was 610 mPas.
[ example 5 ]
1. Preparing an ionic liquid precursor: dissolving octyl pyrrolidone and butane sulfonic acid in a molar ratio of 1: 1.9 in solvent diethyl ether, gradually heating to 100 ℃, stirring for 10h, washing with diethyl ether after the reaction is finished to remove unreacted materials, and drying in vacuum at 70 ℃ for 6h.
2. Preparation of ionic liquid: mixing the washed ionic liquid precursor and methanesulfonic acid according to the molar ratio of 1: 2.0, stirring at 250 ℃ for 12h, and evaporating at 60 ℃ for 0.8h after the reaction is finished to obtain yellow viscous liquid.
The obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 38% of pyrrolidone, 52% of butane sulfonic acid and 10% of p-toluene sulfonic acid group by mass; the ionic liquid catalyst has an electric pH of 2.4 and an electric conductivity of 1.4S/m; the viscosity was 385 mPas.
[ examples 6 to 13 ]
The sulfonic acid functionalized pyrrolidone ionic liquid catalyst described in table 1 can be obtained by operating the sulfonic acid functionalized pyrrolidone ionic liquid according to the preparation conditions of table 1 and the steps in the embodiment.
TABLE 1 preparation conditions for examples 6-13
Examples 14-82 sulfonic acid functionalized pyrrolidone ionic liquid catalysts were used for the production of esters.
The esterification product was obtained by evaluating the performance of the catalyst according to the reaction conditions shown in table 2, using methanol, ethanol, ethylene glycol, n-butanol, propylene glycol, isooctanol, phthalic anhydride, terephthalic acid, naphthalenedicarboxylic acid, and acetic acid as raw materials, and using the sulfonic acid-functionalized pyrrolidone ionic liquid obtained in examples 1 to 13 as a catalyst.
TABLE 2 reaction conditions for examples 14-82
The invention is not the best known technology.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. A preparation method of isooctyl naphthalene dicarboxylate is characterized in that an ionic liquid is used as a catalyst, and the preparation method of the ionic liquid comprises the following steps:
(1) Preparing an ionic liquid precursor: dissolving N-methylpyrrolidone and hexane sulfonic acid in a molar ratio of 1: 1.1 in toluene, gradually heating to 60 ℃, stirring for 7 hours, washing with toluene after the reaction is finished to remove unreacted materials, and vacuum-drying for 6 hours at 50 ℃;
(2) Preparation of ionic liquid: mixing the washed ionic liquid precursor and methanesulfonic acid according to the molar ratio of 1: 1.8, stirring for 8h at 60 ℃, and evaporating for 1h at 60 ℃ after the reaction is finished to obtain yellow viscous liquid; the obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 35% of pyrrolidone, 55% of hexane sulfonic acid and 10% of methylsulfonic acid by mass; the ionic liquid catalyst has an electric pH value of 1.9 and an electric conductivity of 1.35S/m; the viscosity is 450 mPas;
the preparation method takes naphthalenedicarboxylic acid and isooctanol as raw materials, and the molar ratio of the naphthalenedicarboxylic acid to the isooctanol is 1:7.8, the ionic liquid accounts for 3.5 percent of the total mass of the reaction product, the conversion rate of the naphthalenedicarboxylic acid is 100 percent and the yield of the isooctyl alcohol naphthalenedicarboxylate is 99.89 percent when the reaction temperature is 190 ℃, the reaction pressure is 0.15MPa and the reaction time is 2 hours.
2. A preparation method of trimethylene naphthalate is characterized in that an ionic liquid is used as a catalyst, and the preparation method of the ionic liquid comprises the following steps:
(1) Preparing an ionic liquid precursor: dissolving octyl pyrrolidone and butane sulfonic acid in a molar ratio of 1: 1.9 in solvent diethyl ether, gradually heating to 100 ℃, stirring for 10h, washing with diethyl ether after the reaction is finished to remove unreacted materials, and vacuum-drying at 70 ℃ for 6h;
(2) Preparation of ionic liquid: mixing the washed ionic liquid precursor and p-toluenesulfonic acid according to the molar ratio of 1: 2.0, stirring at 250 ℃ for 12h, evaporating at 60 ℃ after the reaction is finished for 0.8h to obtain yellow viscous liquid, wherein the obtained sulfonic acid functionalized pyrrolidone ionic liquid catalyst contains 38% of pyrrolidone, 52% of butane sulfonic acid and 10% of p-toluenesulfonic acid; the ionic liquid catalyst has an electric pH of 2.4 and an electric conductivity of 1.4S/m; viscosity 385mPa · s;
the preparation method takes naphthalenedicarboxylic acid and propylene glycol as raw materials, wherein the molar ratio of the naphthalenedicarboxylic acid to the propylene glycol is 1:7.5, the ionic liquid accounts for 4 percent of the total mass of the reaction product, the conversion rate of the naphthalenedicarboxylic acid is 100 percent at the reaction temperature of 160 ℃, the reaction pressure of 0.07MPa and the reaction time of 6h, and the yield of the trimethylene naphthalate product is 99.67 percent.
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| CN101024613B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alochol acid esterization by sulfonic-acid-radical functionized ion liquid |
| CN100513394C (en) * | 2007-03-23 | 2009-07-15 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| CN101838198A (en) * | 2010-05-13 | 2010-09-22 | 北京***鼎科技有限公司 | Method for preparing carboxylic ester |
| CN102786395B (en) * | 2012-07-18 | 2014-10-29 | 常州大学 | Method for preparation of polyoxymethylene dimethyl ethers through catalysis of pyrrolidone ionic liquid |
| CN107597184B (en) * | 2017-08-15 | 2019-12-06 | 常州大学 | Preparation method and application of iron-based pyrrolidone ionic liquid catalyst |
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