CN113666850B - Preparation method and application of organic sulfonic acid - Google Patents
Preparation method and application of organic sulfonic acid Download PDFInfo
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- CN113666850B CN113666850B CN202110676432.4A CN202110676432A CN113666850B CN 113666850 B CN113666850 B CN 113666850B CN 202110676432 A CN202110676432 A CN 202110676432A CN 113666850 B CN113666850 B CN 113666850B
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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Abstract
The invention relates to the technical field of fine chemicals, in particular to a preparation method and application of organic sulfonic acid. The preparation method of the organic sulfonic acid comprises the following specific steps: s1, preparing organic sulfonate; s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product; s3, purifying the crude organic sulfonic acid product to obtain a finished product. The organic sulfonic acid obtained by the invention has the following advantages: (1) Adopting a gaseous proton donor to improve the production efficiency in the actual reaction process and obtain a polyhydroxy alkane sulfonic acid product with high reaction yield; (2) Adopting enamel thin film evaporation and short-path molecular distillation equipment to process and purify, and effectively separating acidic byproducts and water in the liquid components of the reaction product to obtain a polyhydroxy alkane sulfonic acid finished product with the water content as low as 0.3 percent; (3) The purification and separation process can realize the recovery of hydrochloric acid and the industrialized mass production of the polyhydroxyalkane sulfonic acid while obtaining polyhydroxyalkane sulfonic acid.
Description
Technical Field
The invention relates to the technical field of fine chemicals, in particular to a preparation method and application of organic sulfonic acid.
Background
The aqueous polyurethane is novel polyurethane which uses water as a dispersion medium instead of an organic solvent, and has the advantages of safety, reliability, environmental friendliness, excellent performance, easiness in processing and the like. The aqueous polyurethane may be classified into anionic, cationic and nonionic aqueous polyurethane according to the nature of the hydrophilic group of polyurethane, wherein the anionic polyurethane may be further classified into carboxylic acid type aqueous polyurethane and sulfonic acid type aqueous polyurethane according to the difference of chain extenders. The type of the waterborne polyurethane commonly used in the market at present is carboxylic acid type waterborne polyurethane, and sulfonic acid type waterborne polyurethane is not popularized in China yet; compared with carboxylic acid type waterborne polyurethane, the sulfonic acid type waterborne polyurethane has the characteristics of high storage stability, strong process controllability, low emulsion viscosity, high solid content and the like, and the exploration of the sulfonic acid type waterborne polyurethane has important significance for promoting the industrial development of the polyurethane field.
The waterborne polyurethane is obtained by addition polymerization of substances such as oligomer dihydric alcohol, polyfunctional cyanate, chain extender and the like, wherein the chain extender is various in types, and the property of the characteristic group directly influences the performance of the waterborne polyurethane. Polyhydroxyalkanesulfonic acid is a sulfonic acid compound containing a plurality of hydroxyl groups, and because of its structure containing active hydroxyl groups and sulfonic acid groups, it can be widely used in the fields of polyurethane, lithium battery additives, plating additives, lubricating oil additives, ion exchange resins, emulsifiers, etc., and has gradually become a market research hotspot. The existing polyhydroxyalkane sulfonic acid has the disadvantages of complex preparation process, large risk coefficient, high cost and limited strong hydrophilicity of sulfonic acid, and the dihydroxyalkane sulfonic acid product obtained by the conventional preparation method often has higher water content, which affects the subsequent operation. Based on the above, the preparation of polyhydroxy sulfonic acid with high purity, low water content and convenient process is a problem to be solved in the field.
Disclosure of Invention
The invention solves the problems of complex preparation technology, high operation risk coefficient and high water content of products in the prior art by providing the preparation method of the organic sulfonic acid, and realizes the method of the polyhydroxy alkane sulfonic acid which has high purity, low water content and convenient process and can be industrially produced in large quantities.
The first aspect of the invention provides a preparation method of organic sulfonic acid, wherein the organic sulfonic acid has the structural general formula ofWherein Ra, rb and Rc contain at least 2 hydroxyl groups; ra, rb and Rc may be the same or different;
the preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
In a preferred embodiment, the preparation of the organic sulfonate in the step S1 is specifically that halogenated hydroxyl sulfonate is mixed with strong base weak acid salt, and reflux reaction is carried out for 4-7 hours at 75-100 ℃ to obtain the organic sulfonate.
In a preferred embodiment, the preparation of the organic sulfonate in the step S1 is specifically that unsaturated polyol and acid salt are mixed and reacted for 2 to 6 hours at 35 to 45 ℃ to obtain the organic sulfonate.
In a preferred embodiment, the proton donating donor is an acid gas; the acid gas is a non-metal oxide or a non-metal hydride.
In a preferred embodiment, the step S2 specifically includes introducing a proton donor into the organic sulfonate prepared in the step S1, and reacting until no solid is separated out to obtain a first mixture; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
In a preferred embodiment, the S3 purification operation is that the crude organic sulfonic acid product is added into a physical state converter, the physical state converter separates the crude organic sulfonic acid product into a low boiling point component and a high boiling point component, and the high boiling point component is collected, namely, the purified organic sulfonic acid product.
In a preferred embodiment, the step S3 specifically includes introducing the crude organic sulfonic acid product into a thin film evaporator, separating the crude organic sulfonic acid product into a high-boiling component and a low-boiling component by flowing the crude organic sulfonic acid product through a heating surface of the thin film evaporator, introducing the high-boiling component into a distillation device, and separating impurities to obtain a finished organic sulfonic acid product.
In a preferred embodiment, the thin film evaporator is operated at a temperature of 80 to 120℃and a vacuum of 1 to 10mbar.
In a preferred embodiment, the distillation apparatus is operated at a temperature of from 80 to 150℃and a vacuum of from 0.001 to 1mbar.
In a second aspect, the invention provides the use of a method for the preparation of an organic sulphonic acid in the fields of polyurethane, catalysts, surfactants, ion exchange resins and chemical additives.
The beneficial effects are that:
the method for preparing the organic sulfonic acid has the following advantages:
(1) The gaseous proton donor and polyhydroxy alkane sulfonate are adopted to react in an aqueous solution system, the generated byproducts are directly separated out in a saturated acid solution, the effective separation of solid and liquid components in the reaction process can be realized without recrystallization operation and direct filtration, and the polyhydroxy alkane sulfonic acid product with high reaction yield is obtained while the production efficiency in the actual reaction process is improved;
(2) Purifying the crude polyhydroxyalkane sulfonic acid product by enamel thin film evaporation and short-path molecular distillation equipment, and effectively separating acidic byproducts and water in the liquid component of the reaction product to obtain a polyhydroxyalkane sulfonic acid finished product with the water content as low as 0.3%;
(3) The method has the advantages that hydrochloric acid can be recovered while polyhydroxy alkane sulfonic acid is obtained in the purification and separation process, the method is further used for preparing hydrogen chloride gas, the cyclic operation of the product preparation process is realized, the production efficiency of polyhydroxy alkane sulfonic acid is improved under safe and mild reaction conditions, the reaction process is simple and reliable, the cost is reduced, the actual technical operability is high, and the industrial mass production of polyhydroxy alkane sulfonic acid is realized.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
Approximating language, in the specification and claims, may be applied to modify an amount that would not limit the invention to the specific amount, but would include an acceptable portion that would be close to the amount without resulting in a change in the basic function involved. Accordingly, the modification of a numerical value with "about", "about" or the like means that the present invention is not limited to the precise numerical value. In some examples, the approximating language may correspond to the precision of an instrument for measuring the value. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
In order to solve the problems, the first aspect of the invention provides a preparation method of organic sulfonic acid, wherein the organic sulfonic acid has the structural general formula ofWherein Ra, rb and Rc contain at least 2 hydroxyl groups; ra, rb and Rc may be the same or different;
the preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
In some preferred embodiments, the preparation of the organic sulfonate in the step S1 is specifically that halogenated hydroxyl sulfonate is mixed with strong base weak acid salt, and reflux reaction is carried out for 4-7 hours at 75-100 ℃ to obtain the organic sulfonate.
Further preferably, the halogenated hydroxyl sulfonate has 2 to 6 carbon atoms; still more preferably, the halogenated hydroxyl sulfonate has 3 to 4 carbon atoms.
Examples of halogenated hydroxyl sulfonates include, but are not limited to, sodium 1-chloro-2-hydroxy-3-propanesulfonate, sodium 4-chloro-1-hydroxy-butanesulfonate.
Further preferably, the strong base weak acid salt comprises at least one of sodium carbonate, sodium acetate, sodium phosphate, sodium bicarbonate, sodium sulfide, sodium hydrosulfide, potassium carbonate, potassium bicarbonate, potassium sulfide, and calcium bicarbonate.
Still more preferably, the weight ratio of the halogenated hydroxyl sulfonate to the strong base weak acid salt is 2: (1-1.5).
Preferably, in the step S1, the halogenated hydroxyl sulfonate and the strong alkali weak acid salt are added into a three-neck flask, a sufficient amount of water is added, and the mixture is subjected to reflux stirring reaction for 4-7 hours at the temperature of 75-100 ℃ to obtain the organic sulfonate.
Further preferably, the hydroxyl number of the organic sulfonate is not less than 2.
In some preferred embodiments, the organic sulfonate is prepared in step S1 by mixing an unsaturated polyol with an acid salt and reacting at 35-45℃for 2-6 hours to obtain the organic sulfonate.
Further preferably, the unsaturated polyol has 2 to 6 carbon atoms.
Examples of unsaturated polyols include, but are not limited to, at least one of N, N-bis (2-hydroxyethyl) -2-aminopropene, trimethylolpropane monoallyl ether, 1, 4-dihydroxy-2-butene, 2-pentene-1, 5-diol.
Further preferably, the acid salt is a bisulphite; as examples of bisulfites, sodium bisulfites are included, but are not limited to.
Preferably, in the step S1, the bisulphite is dissolved in water, and is adjusted to be neutral by an alkaline substance, then the unsaturated polyol is added, and the reaction is stirred for 2-5 hours at the temperature of 35-55 ℃, and the ph=7 is controlled by using dilute hydrochloric acid in the reaction process.
In some preferred embodiments, the proton donating donor is an acid gas; the acid gas is a non-metal oxide or a non-metal hydride.
Further preferably, the acid gas is a non-metal hydride.
Examples of nonmetallic hydrides include, but are not limited to, hydrogen chloride gas.
In some preferred embodiments, the step S2 specifically includes introducing a proton donor into the organic sulfonate prepared in the step S1, and reacting until no solid is separated out to obtain a mixture one; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
Further preferably, the proton donor is introduced at a rate of 0.5 to 5L/min.
In some preferred embodiments, the S3 purification operation is performed by adding the crude organic sulfonic acid product to a physical state converter, separating the crude organic sulfonic acid product into a low boiling point component and a high boiling point component by the physical state converter, and collecting the high boiling point component, i.e., obtaining a purified organic sulfonic acid product.
In some preferred embodiments, the step S3 specifically includes introducing the crude organic sulfonic acid product into a thin film evaporator, separating the crude organic sulfonic acid product into a high boiling point component and a low boiling point component by flowing the crude organic sulfonic acid product through a heating surface of the thin film evaporator, introducing the high boiling point component into a distillation device, and separating impurities to obtain a finished organic sulfonic acid product.
In some preferred embodiments, the thin film evaporator operates at a temperature of 80 to 120℃and a vacuum of 1 to 10mbar.
In some preferred embodiments, the distillation apparatus operates at a temperature of 80 to 150℃and a vacuum of 0.001 to 1mbar.
In the invention, on the one hand, based on the characteristic that strong alkali weak acid salt is easy to hydrolyze, polyhydroxy alkane sulfonate can be obtained by reacting with halogenated hydroxyl sulfonate; on the other hand, the sulfonation of the organic compound can be realized by adopting the addition of the low-chain enol and the bisulfite; both methods allow for the preparation of polyhydroxyalkanesulfonates in the organic sulfonic acid synthetic route. The applicant further researches and discovers that when the polyhydroxyalkanoate sulfonate is converted into the sulfonic acid, a gaseous proton donor is adopted to react with the polyhydroxyalkanoate sulfonate in an aqueous medium, solid products are rapidly separated out in a saturated acid solution while the sulfonate in the system is converted into the sulfonic acid, a high-purity liquid component can be obtained through direct filtration, the content of impurity metal ions in the liquid component is extremely low through element analysis, and the process can realize solid-liquid separation while generating the sulfonic acid without carrying out recrystallization operation after the reaction is finished.
The applicant has found through a great deal of experimental investigation that the use of a physical state converter, particularly an enamel thin film evaporation and short path molecular distillation apparatus, in combination with a liquid component, is effective in separating polyhydroxyalkanesulfonic acid, hydrogen chloride, water and hydrochloric acid solutions. In the actual purification process, firstly introducing the crude organic sulfonic acid product into an enamel thin film evaporator, separating the crude organic sulfonic acid product into a high-boiling-point component and a low-boiling-point component through a heating surface of the thin film evaporator, and collecting the high-boiling-point component; compared with other evaporators, the liquid components are temporarily retained on the heating plate and then are separated into the gas and liquid independent channels after entering the enamel thin film evaporator, the resistance of the material thin film in a turbulent state is reduced by the higher evaporation area, the material is stably pushed in a spiral shape under the vacuum condition, the low-boiling acidic byproducts and water flow out from the gas channel, the high-boiling polyhydroxy alkane sulfonic acid flows out from the liquid channel, and the purity of the polyhydroxy alkane sulfonic acid is effectively improved. The method is limited by extremely strong hydrophilicity of the sulfonic acid compound, a small amount of water is still reserved in the collected high-boiling-point component, the collected high-boiling-point component is further introduced into short-range molecular distillation equipment, the polyhydroxyalkanesulfonic acid and residual water move from an evaporation interface to a condensation plate in a short free range, the separation degree of the polyhydroxyalkanesulfonic acid and water molecules is further improved, and a polyhydroxyalkanesulfonic acid product with high purity and low water content is obtained under the process conditions of safety, mildness and lower energy consumption.
The invention can recycle hydrochloric acid while obtaining polyhydroxy alkane sulfonic acid in the purification and separation process, is further used for preparing hydrogen chloride gas, realizes the cyclic operation of the product preparation process, improves the production efficiency of polyhydroxy alkane sulfonic acid under safe and mild reaction conditions, has simple and reliable reaction process and low cost, has high feasibility of practical operation of the technology, and can realize the industrialized mass production of polyhydroxy alkane sulfonic acid.
In a second aspect, the invention provides the use of a method for the preparation of an organic sulphonic acid for use in the fields of polyurethane synthesis, catalysts, surfactants, ion exchange resins and chemical additives.
Examples
In order to better understand the above technical solution, the following describes the above technical solution in detail with reference to specific embodiments. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure. In addition, the raw materials used are commercially available, and the extraction methods of the extracts are conventional extraction methods, unless otherwise specified.
Example 1.
The embodiment provides a preparation method of organic sulfonic acid, wherein the structural formula of the organic sulfonic acid is as followsThe preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
The preparation method of the organic sulfonate in the step S1 comprises the steps of adding 1-chloro-2-hydroxy-3-propanesulfonic acid sodium salt (CAS number is 126-83-0) and sodium carbonate into a three-neck flask, adding water, and carrying out reflux stirring reaction for 5 hours at the temperature of 85 ℃ to obtain the organic sulfonate; the molar ratio of the sodium 1-chloro-2-hydroxy-3-propanesulfonate, sodium carbonate and water is 2:1.2:36.
the proton donor is hydrogen chloride gas;
the step S2 is specifically that a proton donor is introduced into the organic sulfonate and reacts until no solid is separated out, so as to obtain a mixture I; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
The introduction speed of the proton donor is 3L/min.
And S3, introducing the crude organic sulfonic acid product into an enamel thin film evaporator, separating the crude organic sulfonic acid product into a high-boiling-point component and a low-boiling-point component through a heating surface of the enamel thin film evaporator, introducing the high-boiling-point component into a short-range molecular distillation device, and removing water to obtain an organic sulfonic acid finished product.
The working temperature of the enamel thin film evaporator is 110 ℃, and the vacuum degree is 10mBar.
The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01mBar.
Example 2.
The embodiment provides a preparation method of organic sulfonic acid, wherein the structural formula of the organic sulfonic acid is as followsThe preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
The preparation method of the organic sulfonate in the step S1 comprises the steps of mixing sodium bisulphite and water, stirring and dissolving, adjusting the pH value to be 7 by using a sodium hydroxide aqueous solution, then adding 1, 4-butylene glycol, stirring and reacting for 3 hours at the temperature of 40 ℃, and controlling the pH value to be 7 by using dilute hydrochloric acid in the reaction process until the reaction is finished to obtain the organic sulfonate; the molar ratio of the sodium bisulphite to the 1, 4-butylene glycol to the water is 1.4:1:12.4.
the proton donor is hydrogen chloride gas.
The step S2 is specifically that a proton donor is introduced into the organic sulfonate and reacts until no solid is separated out, so as to obtain a mixture I; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
The introduction speed of the proton donor is 3L/min.
And S3, introducing the crude organic sulfonic acid product into an enamel thin film evaporator, separating the crude organic sulfonic acid product into a high-boiling-point component and a low-boiling-point component through a heating surface of the enamel thin film evaporator, introducing the high-boiling-point component into a short-range molecular distillation device, and removing water to obtain an organic sulfonic acid finished product.
The working temperature of the enamel thin film evaporator is 110 ℃, and the vacuum degree is 10mBar.
The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01mBar.
Example 3.
The embodiment provides a preparation method of organic sulfonic acid, wherein the structural formula of the organic sulfonic acid is as followsThe preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
The preparation method of the organic sulfonate in the step S1 comprises the steps of adding sodium 4-chloro-1-hydroxy-butane sulfonate (CAS number 54322-20-2) and sodium carbonate into a three-neck flask, adding water, and carrying out reflux stirring reaction for 5 hours at the temperature of 85 ℃ to obtain the organic sulfonate; the molar ratio of the sodium 4-chloro-1-hydroxy-butane sulfonate, sodium carbonate and water is 2:1.2:36.
the proton donor is hydrogen chloride gas.
The step S2 is specifically that a proton donor is introduced into the organic sulfonate and reacts until no solid is separated out, so as to obtain a mixture I; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
The introduction speed of the proton donor is 3L/min.
And S3, introducing the crude organic sulfonic acid product into an enamel thin film evaporator, separating the crude organic sulfonic acid product into a high-boiling-point component and a low-boiling-point component through a heating surface of the enamel thin film evaporator, introducing the high-boiling-point component into a short-range molecular distillation device, and removing water to obtain an organic sulfonic acid finished product.
The working temperature of the enamel thin film evaporator is 110 ℃, and the vacuum degree is 10mBar.
The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01mBar.
Example 4.
This example provides a method for preparing an organic sulfonic acid, and the specific embodiment is the same as example 1; the difference is that: the working temperature of the enamel thin film evaporator is 100 ℃, and the vacuum degree is 10mBar.
Example 5.
This example provides a method for preparing an organic sulfonic acid, and the specific embodiment is the same as example 1; the difference is that: the working temperature of the short-path molecular distillation device is 110 ℃, and the vacuum degree is 0.01mBar.
Comparative example 1.
The embodiment provides a preparation method of organic sulfonic acid, wherein the structural formula of the organic sulfonic acid is as followsThe preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
The preparation method of the organic sulfonate in the step S1 comprises the steps of adding 1-chloro-2-hydroxy-3-propanesulfonic acid sodium salt (CAS number is 126-83-0) and sodium carbonate into a three-neck flask, adding water, and carrying out reflux stirring reaction for 5 hours at the temperature of 85 ℃ to obtain the organic sulfonate; the molar ratio of the sodium 1-chloro-2-hydroxy-3-propanesulfonate, sodium carbonate and water is 2:1.2:36.
the proton donor is a concentrated aqueous hydrochloric acid solution with a mass fraction of about 37%.
The step S2 is specifically that organic sulfonate and a proton donor are mixed and reacted for 6 hours to obtain a mixture I; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
And S3, introducing the crude organic sulfonic acid product into an enamel thin film evaporator, separating the crude organic sulfonic acid product into a high-boiling-point component and a low-boiling-point component through a heating surface of the enamel thin film evaporator, introducing the high-boiling-point component into a short-range molecular distillation device, and removing water to obtain an organic sulfonic acid finished product.
The working temperature of the enamel thin film evaporator is 110 ℃, and the vacuum degree is 10mBar.
The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01mBar.
Comparative example 2.
The embodiment provides a preparation method of organic sulfonic acid, wherein the structural formula of the organic sulfonic acid is as followsThe preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product.
The preparation method of the organic sulfonate in the step S1 comprises the steps of adding 1-chloro-2-hydroxy-3-propanesulfonic acid sodium salt (CAS number is 126-83-0) and sodium carbonate into a three-neck flask, adding water, and carrying out reflux stirring reaction for 5 hours at the temperature of 85 ℃ to obtain the organic sulfonate; the molar ratio of the sodium 1-chloro-2-hydroxy-3-propanesulfonate, sodium carbonate and water is 2:1.2:36.
the proton donor is hydrogen chloride gas;
the step S2 is specifically that a proton donor is introduced into the organic sulfonate and reacts until no solid is separated out, so as to obtain a mixture I; the mixture I is filtered to obtain the crude product of the organic sulfonic acid.
The introduction speed of the proton donor is 3L/min.
And step S3, specifically, introducing the crude product of the organic sulfonic acid into a vacuum rotary evaporator, and removing hydrogen chloride and water through vacuum rotary evaporation under the conditions of 110 ℃ and the vacuum degree of 10mBar to obtain a finished product of the organic sulfonic acid.
Performance test method
Water content:
the water content of the organic sulfonic acid finished products prepared in examples 1-5 and comparative examples 1-2 was measured using a karl fischer moisture analyzer.
Product yield and impurity content:
the product yields of the organic sulfonic acids prepared in examples 1-5 and comparative examples 1-2 were determined by an acid-base titration method using potassium hydroxide standard solution to titrate an ethanol solution of the organic sulfonic acid, and the calculation formula is:
wherein: c is the concentration of potassium hydroxide standard solution, and the unit is mol/L;
v is the volume of the potassium hydroxide standard solution consumed by the sample, and the unit is mL;
m is the relative molecular mass of organic sulfonic acid, and the unit is 1;
m is the mass of the sample, and the unit is g;
the content of impurity sodium in the finished product is tested by referring to JY/T015-1996 standard, and the content of chlorine is tested by referring to BS EN 14582:2016 standard.
Performance test data
TABLE 1 Performance test results
Finally, it is pointed out that the foregoing examples are illustrative only and serve to explain some of the features of the method according to the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (1)
1. A preparation method of organic sulfonic acid is characterized in that the structural formula of the organic sulfonic acid is
The preparation method of the organic sulfonic acid comprises the following specific steps:
s1, preparing organic sulfonate;
s2, reacting the organic sulfonate with a proton donor to obtain an organic sulfonic acid crude product;
s3, purifying the crude organic sulfonic acid product to obtain a finished product;
the preparation method of the organic sulfonate in the step S1 comprises the steps of adding 1-chloro-2-hydroxy-3-propane sodium sulfonate and sodium carbonate into a three-neck flask, adding water, and carrying out reflux stirring reaction for 5 hours at the temperature of 85 ℃ to obtain the organic sulfonate; the molar ratio of the sodium 1-chloro-2-hydroxy-3-propanesulfonate, sodium carbonate and water is 2:1.2:36;
the proton donor is hydrogen chloride gas;
the step S2 is specifically that a proton donor is introduced into the organic sulfonate and reacts until no solid is separated out, so as to obtain a mixture I; filtering the mixture I to obtain an organic sulfonic acid crude product;
the charging speed of the proton donor is 3L/min;
the step S3 is that firstly, the crude product of the organic sulfonic acid is introduced into an enamel thin film evaporator, the crude product of the organic sulfonic acid is separated into a high boiling point component and a low boiling point component through a heating surface of the enamel thin film evaporator, the high boiling point component is introduced into a short-range molecular distillation device, and the moisture is removed, so that a finished product of the organic sulfonic acid is obtained;
the working temperature of the enamel thin film evaporator is 110 ℃, and the vacuum degree is 10mBar;
the working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01mBar.
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