阅读说明：本技术 一种有机磺酸的制备方法及其应用 (Preparation method and application of organic sulfonic acid ) 是由 吴后胜 汤嘉陵 苏始朝 张崇照 于 2021-06-18 设计创作，主要内容包括：本发明涉及精细化学品技术领域,尤其涉及一种有机磺酸的制备方法及其应用。所述有机磺酸的具体制备步骤包括：S1.制备有机磺酸盐；S2.将有机磺酸盐与质子提供体反应,得到有机磺酸粗产物；S3.纯化有机磺酸粗产物,得到成品。本发明得到的有机磺酸具有以下优点：(1)采用气态质子提供体,提高实际反应过程中的生产效率的同时得到高反应收率的多羟基链烷磺酸产物；(2)采用搪瓷薄膜蒸发和短程分子蒸馏设备处理提纯,有效分离反应产物液体组分中的酸性副产物和水,得到含水率低至0.3％的多羟基链烷磺酸成品；(3)提纯分离过程得到多羟基链烷磺酸的同时能够实现盐酸的回收,实现多羟基链烷磺酸的工业化量产。(The invention relates to the technical field of fine chemicals, in particular to a preparation method and application of organic sulfonic acid. The specific preparation steps of the organic sulfonic acid comprise: s1, preparing organic sulfonate; s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product; and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product. The organic sulfonic acid obtained by the invention has the following advantages: (1) the gaseous proton donor is adopted, so that the production efficiency in the actual reaction process is improved, and meanwhile, the polyhydroxyalkane sulfonic acid product with high reaction yield is obtained; (2) adopting enamel film evaporation and short-path molecular distillation equipment for treatment and purification, effectively separating acidic byproducts and water in liquid components of reaction products, and obtaining polyhydroxy alkane sulfonic acid finished products with the water content of 0.3 percent; (3) the purification and separation process can realize the recovery of hydrochloric acid while obtaining the polyhydroxyalkanesulfonic acid, and realize the industrial mass production of the polyhydroxyalkanesulfonic acid.)

1. The preparation method of the organic sulfonic acid is characterized in that the structural general formula of the organic sulfonic acid is

Wherein Ra, Rb and Rc contain at least 2 hydroxyl groups;

ra, Rb and Rc may be the same or different;

the specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

2. The method of claim 1, wherein the step of S1 is performed by mixing a halogenated hydroxy sulfonate with a strong base and a weak acid salt, and performing a reflux reaction at 75-100 ℃ for 4-7 hours to obtain an organic sulfonate.

3. The method for preparing organic sulfonic acid according to claim 1, wherein the step of S1 is to prepare organic sulfonate by mixing unsaturated polyol and acid salt and reacting at 35-45 ℃ for 2-6 h.

4. The process according to any one of claims 1 to 3, wherein the proton donor is an acid gas; the acid gas is a non-metal oxide or a non-metal hydride.

5. The method for preparing organic sulfonic acid according to any one of claims 1 to 4, wherein the step S2 is specifically that a proton donor is introduced into the organic sulfonate prepared in the step S1, and the reaction is carried out until no solid is precipitated, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

6. The method according to claim 1, wherein the purification operation of S3 is to add the crude product of organic sulfonic acid into a physical converter, the physical converter separates the crude product of organic sulfonic acid into a low boiling point component and a high boiling point component, and the high boiling point component is collected as the purified finished product of organic sulfonic acid.

7. The method according to claim 6, wherein the step S3 comprises feeding the crude organic sulfonic acid product into a thin film evaporator, passing the crude organic sulfonic acid product through a heating surface of the thin film evaporator to separate the crude organic sulfonic acid product into a high-boiling component and a low-boiling component, feeding the high-boiling component into a distillation apparatus, and separating impurities to obtain the final organic sulfonic acid product.

8. The method according to claim 7, wherein the thin film evaporator has an operating temperature of 80 to 120 ℃ and a vacuum of 1 to 10 mbar.

9. The process according to claim 7 or 8, wherein the distillation apparatus is operated at a temperature of 80 to 150 ℃ and a vacuum of 0.001 to 1 mbar.

10. Use of a process for the preparation of organic sulfonic acids according to any one of claims 1 to 9 in the fields of polyurethane synthesis, catalysts, surfactants, ion exchange resins and chemical additives.

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 waterborne polyurethane is a novel polyurethane which takes 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. According to the property of hydrophilic groups of polyurethane, the aqueous polyurethane can be divided into anionic polyurethane, cationic polyurethane and nonionic aqueous polyurethane, wherein the anionic polyurethane can be further divided into carboxylic acid type aqueous polyurethane and sulfonic acid type aqueous polyurethane according to the difference of chain extenders. The type of the water-based polyurethane commonly used in the market at present is carboxylic acid type water-based polyurethane, and sulfonic acid type water-based polyurethane is not popularized yet at home; 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 in the polyurethane field.

The waterborne polyurethane is obtained by the addition polymerization of substances such as oligomer dihydric alcohol, polyfunctional cyanate ester, chain extenders and the like, wherein the types of the chain extenders are various, and the properties of characteristic groups directly influence the performance of the waterborne polyurethane. The polyhydroxyalkanesulfonic acid is a sulfonic acid compound containing a plurality of hydroxyl groups, and the structure of the polyhydroxyalkanesulfonic acid contains active hydroxyl groups and sulfonic acid groups, so that the polyhydroxyalkanesulfonic acid can be widely applied to the fields of polyurethane, lithium battery additives, electroplating additives, lubricating oil additives, ion exchange resins, emulsifiers and the like, and is gradually a market research hotspot. The existing preparation process of polyhydroxyalkane sulfonic acid is complex, has large danger coefficient and high cost, is limited by strong hydrophilicity of sulfonic acid, and the dihydroxyalkane sulfonic acid product obtained by the conventional preparation method often has higher water content and influences subsequent operation. Based on this, the preparation of the polyhydroxysulfonic acid with high purity, low water content and convenient process becomes an urgent problem to be solved in the field.

Disclosure of Invention

The invention provides a preparation method of organic sulfonic acid, solves the problems of complex preparation technology of polyhydroxyalkane sulfonic acid, high operation risk coefficient and high and constant water content of products in the prior art, and realizes a polyhydroxyalkane sulfonic acid method which can be used for industrial mass production and has high purity, low water content and convenient process.

The invention provides a preparation method of organic sulfonic acid, and the general structural formula of the organic sulfonic acid isWherein RaRb and Rc contain at least 2 hydroxyl groups; ra, Rb and Rc may be the same or different;

the specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

In a preferred embodiment, the step S1 for preparing the organic sulfonate is to mix the halogenated hydroxyl sulfonate with the strong base weak acid salt, and reflux-react at 75-100 ℃ for 4-7h to obtain the organic sulfonate.

In a preferred embodiment, the step of S1 for preparing the organic sulfonate is to mix the unsaturated polyol and the acid salt and react at 35-45 ℃ for 2-6h to obtain the organic sulfonate.

In a preferred embodiment, the proton 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 is specifically that a proton donor is introduced into the organic sulfonate prepared in the step S1, and the reaction is performed until no solid is precipitated, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

In a preferred embodiment, the S3 purification operation is to add the crude organic sulfonic acid product into a physical state converter, separate the crude organic sulfonic acid product into a low boiling point component and a high boiling point component, and collect the high boiling point component, i.e. the purified finished organic sulfonic acid product.

In a preferred embodiment, the step S3 is specifically that the crude organic sulfonic acid product is first introduced into a thin film evaporator, the crude organic sulfonic acid product is separated into a high boiling point component and a low boiling point component by flowing through a heating surface of the thin film evaporator, the high boiling point component is introduced into a distillation device, and impurities are separated to obtain the finished organic sulfonic acid product.

In a preferred embodiment, the thin-film evaporator has an operating temperature of 80 to 120 ℃ and a vacuum of 1 to 10 mbar.

In a preferred embodiment, the operating temperature of the distillation apparatus is from 80 to 150 ℃ and the vacuum is from 0.001 to 1 mbar.

In a second aspect, the invention provides the use of a process for the preparation of organic sulfonic acids in the fields of polyurethanes, catalysts, surfactants, ion exchange resins and chemical additives.

Has the advantages that:

the method for preparing the organic sulfonic acid has the following advantages:

(1) gaseous proton donor is adopted to react with polyhydroxy alkane sulfonate in an aqueous solution system, the generated by-product is directly separated out in saturated acid solution, recrystallization operation is not needed, and effective separation of solid-liquid components in the reaction process can be realized by direct filtration, so that the polyhydroxy alkane sulfonate product with high reaction yield is obtained while the production efficiency in the actual reaction process is improved;

(2) purifying the crude polyhydroxyalkanesulfonic acid product by enamel thin-film evaporation and short-path molecular distillation equipment, and effectively separating acidic byproducts and water in liquid components of a reaction product to obtain a polyhydroxyalkanesulfonic acid finished product with the water content of 0.3 percent;

(3) the polyhydroxyalkane sulfonic acid is obtained in the purification and separation process, meanwhile, the hydrochloric acid can be recovered, the polyhydroxyalkane sulfonic acid can be further used for preparing hydrogen chloride gas, the cyclic operation of a product preparation process is realized, the production efficiency of the polyhydroxyalkane sulfonic acid is improved under safe and mild reaction conditions, the reaction process is simple, convenient and reliable, the cost is reduced, the technical practical operability is strong, and the industrial mass production of the polyhydroxyalkane sulfonic acid is realized.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. 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, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the above problems, the present invention provides, in a first aspect, a method for preparing an organic sulfonic acid having a general structural formulaWherein Ra, Rb and Rc contain at least 2 hydroxyl groups; ra, Rb and Rc may be the same or different;

the specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

In some preferred embodiments, the step S1 is to prepare the organic sulfonate by mixing the halogenated hydroxy sulfonate with the strong base weak acid salt, and performing reflux reaction at 75-100 ℃ for 4-7h to obtain the organic sulfonate.

More preferably, the number of carbon atoms of the halogenated hydroxysulfonate is 2 to 6; more preferably, the number of carbon atoms of the halogenated hydroxysulfonate is 3 to 4.

Examples of halogenated hydroxysulfonates include, but are not limited to, sodium 1-chloro-2-hydroxy-3-propanesulfonate, sodium 4-chloro-1-hydroxy-butanesulfonate.

Further preferably, the strong alkali and 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, the step S1 is specifically to add halogenated hydroxysulfonate and strong base weak acid salt into a three-neck flask, add enough water, and reflux-stir react for 4 to 7 hours at 75 to 100 ℃ to obtain organic sulfonate.

More preferably, the number of hydroxyl groups of the organic sulfonate is not less than 2.

In some preferred embodiments, the step of S1 is to prepare the organic sulfonate, specifically, the unsaturated polyol is mixed with the acid salt and reacted at 35-45 ℃ for 2-6h to obtain the organic sulfonate.

More 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 bisulfite salt; as an example of the bisulfite, sodium bisulfite is included, but not limited to.

Preferably, the step S1 is specifically to dissolve bisulfite in water, adjust to neutrality with alkaline substances, add unsaturated polyol, and react at 35-55 ℃ for 2-5h with stirring, wherein dilute hydrochloric acid is used to control pH to 7 during the reaction.

In some preferred embodiments, the proton 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 non-metal hydrides include, but are not limited to, hydrogen chloride gas.

In some preferred embodiments, the step S2 is specifically that a proton donor is introduced into the organic sulfonate prepared in the step S1, and the reaction is performed until no solid is precipitated, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

Further preferably, the introduction rate of the proton donor is 0.5 to 5L/min.

In some preferred embodiments, the S3 purification operation is to add the crude organic sulfonic acid product into a physical converter, separate the crude organic sulfonic acid product into a low boiling point component and a high boiling point component, and collect the high boiling point component, i.e. the purified organic sulfonic acid product.

In some preferred embodiments, the step S3 is specifically that the crude organic sulfonic acid product is first introduced into a thin film evaporator, the crude organic sulfonic acid product is separated into a high boiling point component and a low boiling point component by flowing through a heating surface of the thin film evaporator, the high boiling point component is introduced into a distillation apparatus, and impurities are separated to obtain the finished organic sulfonic acid product.

In some preferred embodiments, the thin film evaporator has an operating temperature of 80 to 120 ℃ and a vacuum of 1 to 10 mbar.

In some preferred embodiments, the distillation apparatus is operated at a temperature of from 80 to 150 ℃ and a vacuum of from 0.001 to 1 mbar.

The invention discovers that on the one hand, on the basis of the characteristic that strong base and weak acid salt are 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 adding low-alkene alcohol and bisulfite; both methods allow the preparation of polyhydroxyalkanesulfonates in organic sulfonic acid synthesis routes. The applicant further researches and discovers that when the polyhydroxyalkane sulfonate is converted into the sulfonic acid, a gaseous proton donor is adopted to react with the polyhydroxyalkane sulfonate in an aqueous solution medium, a solid product is rapidly separated out in a saturated acid solution while the sulfonate is converted into the sulfonic acid in the system, and a high-purity liquid component can be obtained by direct filtration.

The applicant has found through a great deal of experimental studies that the use of a physical state converter for the liquid component, in particular an enamel thin film evaporator and a short path molecular distillation apparatus together, enables the effective separation of polyhydroxyalkanesulfonic acid, hydrogen chloride, water and hydrochloric acid solution. In the actual purification process, firstly, introducing an organic sulfonic acid crude product into an enamel film evaporator, separating the organic sulfonic acid crude product into a high-boiling-point component and a low-boiling-point component by flowing through a heating surface of the film evaporator, and collecting the high-boiling-point component; compared with other evaporators, the liquid components are separated and enter the gas-liquid independent channels after being temporarily retained on the heating plate after entering the enamel film evaporator, the higher evaporation area enables the resistance of a material film in a turbulent flow state to be lower, the material is stably propelled in a spiral shape under the vacuum condition, the low-boiling acid by-products and water flow out from the gas channel, the high-boiling polyhydroxyalkanesulfonic acid flows out from the liquid channel, and the purity of the polyhydroxyalkanesulfonic acid is effectively improved. Limited by the extremely strong hydrophilicity of the sulfonic acid compound, a small amount of water is still remained in the collected high-boiling-point component, and the collected high-boiling-point component is further introduced into short-path molecular distillation equipment, so that the polyhydroxyalkanesulfonic acid and the residual water move to a condensation plate from an evaporation interface in a short free path, the separation degree of the polyhydroxyalkanesulfonic acid and water molecules is further improved, and the polyhydroxyalkanesulfonic acid product with high purity and low water content is obtained under the process conditions of safety, mildness and less energy consumption.

The method can realize the recovery of hydrochloric acid while obtaining the polyhydroxyalkanesulfonic acid in the purification and separation process, is further used for preparing hydrogen chloride gas, realizes the circular operation of a product preparation process, improves the production efficiency of the polyhydroxyalkanesulfonic acid under safe and mild reaction conditions, has simple and reliable reaction process, reduces the cost, has high feasibility of technical actual operation, and can realize the industrial mass production of the polyhydroxyalkanesulfonic acid.

In a second aspect, the invention provides the use of a process for the preparation of organic sulfonic acids in the fields of polyurethane synthesis, catalysts, surfactants, ion exchange resins and chemical additives.

Examples

In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the raw materials are commercially available and the extraction methods of the extract are all conventional extraction methods, if not otherwise specified.

Example 1.

This example provides a method for preparing an organic sulfonic acid having the formulaThe specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

The step S1 of preparing the organic sulfonate is specifically that 1-chloro-2-hydroxy-3-propanesulfonic acid sodium salt (CAS number is 126-83-0) and sodium carbonate are added into a three-neck flask, water is added, and reflux stirring reaction is carried out for 5 hours at 85 ℃ to obtain the organic sulfonate; the molar ratio of the 1-chlorine-2-hydroxyl-3-sodium propanesulfonate, the sodium carbonate and the 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 organic sulfonate, and the reaction is carried out until no solid is separated out, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

The introduction speed of the proton donor is 3L/min.

And the step S3 is specifically that the crude product of the organic sulfonic acid is firstly introduced into an enamel film evaporator, the crude product of the organic sulfonic acid flows through the heating surface of the enamel film evaporator to be separated into a high boiling point component and a low boiling point component, the high boiling point component is introduced into a short-path molecular distillation device to remove water, and the finished product of the organic sulfonic acid is obtained.

The working temperature of the enamel film evaporator is 110 ℃, and the vacuum degree is 10 mBar.

The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01 mBar.

Example 2.

This example provides a method for preparing an organic sulfonic acid having the formulaThe specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

The step S1 of preparing the organic sulfonate specifically includes mixing sodium bisulfite with water, stirring for dissolution, adjusting the pH to 7 with an aqueous solution of sodium hydroxide, adding 1, 4-butenediol, stirring for reaction at 40 ℃ for 3 hours, and controlling the pH to 7 with dilute hydrochloric acid during the reaction until the reaction is finished to obtain the organic sulfonate; the molar ratio of the sodium bisulfite, the 1, 4-butylene glycol and 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 organic sulfonate, and the reaction is carried out until no solid is separated out, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

The introduction speed of the proton donor is 3L/min.

And the step S3 is specifically that the crude product of the organic sulfonic acid is firstly introduced into an enamel film evaporator, the crude product of the organic sulfonic acid flows through the heating surface of the enamel film evaporator to be separated into a high boiling point component and a low boiling point component, the high boiling point component is introduced into a short-path molecular distillation device to remove water, and the finished product of the organic sulfonic acid is obtained.

The working temperature of the enamel film evaporator is 110 ℃, and the vacuum degree is 10 mBar.

The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01 mBar.

Example 3.

This example provides a method for preparing an organic sulfonic acid having the formulaThe specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

The step S1 of preparing the organic sulfonate is specifically that 4-chloro-1-hydroxy-butane sodium sulfonate (CAS number 54322-20-2) and sodium carbonate are added into a three-neck flask, water is added, and reflux stirring is carried out at 85 ℃ for 5 hours to obtain the organic sulfonate; the molar ratio of the sodium 4-chloro-1-hydroxy-butanesulfonate, the sodium carbonate and the 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 organic sulfonate, and the reaction is carried out until no solid is separated out, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

The introduction speed of the proton donor is 3L/min.

And the step S3 is specifically that the crude product of the organic sulfonic acid is firstly introduced into an enamel film evaporator, the crude product of the organic sulfonic acid flows through the heating surface of the enamel film evaporator to be separated into a high boiling point component and a low boiling point component, the high boiling point component is introduced into a short-path molecular distillation device to remove water, and the finished product of the organic sulfonic acid is obtained.

The working temperature of the enamel film evaporator is 110 ℃, and the vacuum degree is 10 mBar.

The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01 mBar.

Example 4.

The embodiment provides a preparation method of organic sulfonic acid, and the specific implementation mode is the same as that of embodiment 1; the difference lies in that: the working temperature of the enamel film evaporator is 100 ℃, and the vacuum degree is 10 mBar.

Example 5.

The embodiment provides a preparation method of organic sulfonic acid, and the specific implementation mode is the same as that of embodiment 1; the difference lies in that: the working temperature of the short-path molecular distillation device is 110 ℃, and the vacuum degree is 0.01 mBar.

Comparative example 1.

This example provides a method for preparing an organic sulfonic acid having the formulaThe specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

The step S1 of preparing the organic sulfonate is specifically that 1-chloro-2-hydroxy-3-propanesulfonic acid sodium salt (CAS number is 126-83-0) and sodium carbonate are added into a three-neck flask, water is added, and reflux stirring reaction is carried out for 5 hours at 85 ℃ to obtain the organic sulfonate; the molar ratio of the 1-chlorine-2-hydroxyl-3-sodium propanesulfonate, the sodium carbonate and the water is 2: 1.2: 36.

the proton donor is concentrated hydrochloric acid water solution with mass fraction of about 37%.

The S2 step is specifically that the organic sulfonate and the proton donor are mixed and react for 6 hours to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

And the step S3 is specifically that the crude product of the organic sulfonic acid is firstly introduced into an enamel film evaporator, the crude product of the organic sulfonic acid flows through the heating surface of the enamel film evaporator to be separated into a high boiling point component and a low boiling point component, the high boiling point component is introduced into a short-path molecular distillation device to remove water, and the finished product of the organic sulfonic acid is obtained.

The working temperature of the enamel film evaporator is 110 ℃, and the vacuum degree is 10 mBar.

The working temperature of the short-path molecular distillation device is 130 ℃, and the vacuum degree is 0.01 mBar.

Comparative example 2.

This example provides a method for preparing an organic sulfonic acid having the formulaThe specific preparation steps of the organic sulfonic acid comprise:

s1, preparing organic sulfonate;

s2, reacting organic sulfonate with a proton provider to obtain an organic sulfonic acid crude product;

and S3, purifying the crude product of the organic sulfonic acid to obtain a finished product.

The step S1 of preparing the organic sulfonate is specifically that 1-chloro-2-hydroxy-3-propanesulfonic acid sodium salt (CAS number is 126-83-0) and sodium carbonate are added into a three-neck flask, water is added, and reflux stirring reaction is carried out for 5 hours at 85 ℃ to obtain the organic sulfonate; the molar ratio of the 1-chlorine-2-hydroxyl-3-sodium propanesulfonate, the sodium carbonate and the 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 organic sulfonate, and the reaction is carried out until no solid is separated out, so as to obtain a first mixture; and filtering the mixture I to obtain a crude product of the organic sulfonic acid.

The introduction speed of the proton donor is 3L/min.

And the step S3 is specifically that the crude product of the organic sulfonic acid is introduced into a vacuum rotary evaporator, and hydrogen chloride and water are removed by vacuum rotary evaporation at the temperature of 110 ℃ and the vacuum degree of 10mBar, so that the finished product of the organic sulfonic acid is obtained.

Performance test method

Water content:

the water content of the finished organic sulfonic acids prepared in examples 1 to 5 and comparative examples 1 to 2 was measured by a Karl Fischer moisture analyzer.

Product yield and impurity content:

the product yield of the organic sulfonic acid prepared in examples 1-5 and comparative examples 1-2 was determined by acid-base titration method, which is to titrate an ethanol solution of the organic sulfonic acid with a standard solution of potassium hydroxide, and the calculation formula is:

in the formula: c is the concentration of the standard solution of potassium hydroxide, 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 the organic sulfonic acid and has the unit of 1;

m is the sample mass, and the unit is g;

the content of impurity sodium in the finished product is tested according to JY/T015-.

Performance test data

TABLE 1 Performance test results

Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.