阅读说明：本技术 一种液态磺化剂及其制备方法和应用 (Liquid sulfonating agent and preparation method and application thereof ) 是由 王顺平 冯练享 白清泉 于 2021-01-06 设计创作，主要内容包括：本发明提供了一种液态磺化剂及其制备方法和应用,属于磺化反应技术领域。本发明提供的液态磺化剂,由以下重量份的原料制备得到：氨基磺酸5～8份,尿素3.5～10.5份,助溶剂4～20份；所述助溶剂为氯化胆碱和/或甘油。本发明通过将氨基磺酸和尿素与助溶剂混合,使得氨基磺酸能够在常温下以液态形式存在,用于磺化反应时,可直接以液态形式使用,避免了传统固液反应氨基磺酸和尿素溶解不好的问题,使磺化反应更加均匀、改性更加彻底。此外,将本发明的液态磺化剂用于磺化反应制备加脂剂时,无需添加有机溶剂,对环境友好。(The invention provides a liquid sulfonating agent, a preparation method and application thereof, belonging to the technical field of sulfonation reaction. The liquid sulfonating agent provided by the invention is prepared from the following raw materials in parts by weight: 5-8 parts of sulfamic acid, 3.5-10.5 parts of urea and 4-20 parts of cosolvent; the cosolvent is choline chloride and/or glycerol. According to the invention, through mixing sulfamic acid, urea and the cosolvent, sulfamic acid can exist in a liquid state at normal temperature, and can be directly used in a liquid state when being used for sulfonation reaction, so that the problem of poor dissolution of sulfamic acid and urea in the traditional solid-liquid reaction is avoided, and the sulfonation reaction is more uniform and more thorough in modification. In addition, when the liquid sulfonating agent is used for preparing the fatting agent through sulfonation reaction, an organic solvent is not required to be added, and the environment-friendly effect is achieved.)

1. The liquid sulfonating agent is characterized by being prepared from the following raw materials in parts by weight: 5-8 parts of sulfamic acid, 3.5-10.5 parts of urea and 4-20 parts of cosolvent; the cosolvent is choline chloride and/or glycerol.

2. The liquid sulfonating agent according to claim 1, wherein when the cosolvent is choline chloride, the choline chloride is 4-12 parts by weight based on the weight of the sulfamic acid.

3. The liquid sulfonating agent according to claim 1, wherein when the cosolvent is glycerol, the glycerol is 4-12 parts by weight of the sulfamic acid.

4. The liquid sulfonating agent according to claim 1, wherein when the cosolvent comprises choline chloride and glycerol, the choline chloride is 4-12 parts by weight and the glycerol is greater than 0 and less than or equal to 8 parts by weight based on the weight parts of the sulfamic acid.

5. A process for the preparation of a liquid sulfonating agent as claimed in any one of claims 1 to 4, comprising the steps of:

heating urea and a cosolvent to 20-50 ℃, and stirring until the urea and the cosolvent are completely liquid; and mixing the liquid with sulfamic acid at the temperature of 20-50 ℃ to obtain the liquid sulfonating agent.

6. The application of the liquid sulfonating agent as defined in any one of claims 1 to 4 or the liquid sulfonating agent prepared by the preparation method as defined in claim 5 in preparing a fatliquor by sulfonation reaction.

7. Use according to claim 6, characterized in that said process for preparing a fatliquor comprises the following steps:

adding the sulfonated substance into a reaction kettle, heating to 90-140 ℃, adding a liquid sulfonating agent, and carrying out sulfonation reaction; and cooling the product system of the sulfonation reaction to 50-70 ℃, adding an emulsifier and water, and emulsifying to obtain the fatting agent.

8. The use according to claim 7, wherein the sulfonated substance is a vegetable oil or fat, a higher alcohol or a fatty alcohol ether; the mass ratio of the sulfonated substance to the liquid sulfonating agent is (28-29): (20-22).

9. The use according to claim 7, wherein the emulsifier is a mixture of fatty amide polyoxyethylene ether and sorbitan monooleate polyoxyethylene ether, and the mass ratio of the sulfonated substance to the emulsifier is (28-29): (1-5).

10. The use according to claim 7, wherein the sulfonation reaction is carried out for a period of 1 to 5 hours.

Technical Field

The invention relates to the technical field of sulfonation reaction, in particular to a liquid sulfonating agent and a preparation method and application thereof.

Background

Sulfonation is an important reaction, and in the synthetic fat-liquoring agent material, the sulfonation is commonly used for modification of grease and alcohol so as to improve the hydrophilicity of the grease and alcohol, so that the grease and alcohol can be self-emulsified in water. The sulfonation reactions commonly used are mainly the following: one method is to use concentrated sulfuric acid as a sulfonating agent to modify grease, high-carbon alcohol and the like at normal temperature, but the method adopts excessive concentrated sulfuric acid, and after the reaction is finished, the excessive acid needs to be washed away by saturated salt solution, so that a large amount of acid wastewater is formed, the environmental protection pressure is high, and the concentrated sulfuric acid has strong oxidizability, so careless operators are often injured; one is to utilize sulfur trioxide as a sulfonating agent to react with grease in a tubular reactor, and the method needs to consider the treatment of sulfur trioxide tail gas and needs to be carried out in a special tubular reactor, so that the equipment cost is high, and the method is suitable for continuous high-yield production; and the other method is to use sulfamic acid as a sulfonating agent to react with higher alcohol, fatty alcohol ether and the like under the catalytic action of urea, the method can be carried out by adopting a conventional reaction kettle, three wastes are not generated, and the method is a better sulfonation method, but the method belongs to a solid-liquid reaction, the sulfamic acid and the urea are both solid, the reaction is often incomplete in the reaction process, the poor hydrophilicity of the product cannot meet the modification requirement, and the like, so the application range is not wide enough.

Disclosure of Invention

The invention aims to provide a liquid sulfonating agent and a preparation method and application thereof, the liquid sulfonating agent takes sulfamic acid as the sulfonating agent, and can be directly added into sulfonation reaction, so that the reaction is more uniform, the modification is more thorough, and the problem of poor solid dissolution of solid-liquid reaction is avoided; meanwhile, an organic solvent is not required to be added to dissolve the materials, so that the method is environment-friendly.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a liquid sulfonating agent, which is prepared from the following raw materials in parts by weight: 5-8 parts of sulfamic acid, 3.5-10.5 parts of urea and 4-20 parts of cosolvent; the cosolvent is choline chloride and/or glycerol.

Preferably, when the cosolvent is choline chloride, the choline chloride is 4-12 parts by weight based on the weight part of the sulfamic acid.

Preferably, when the cosolvent is glycerol, the glycerol is 4-12 parts by weight based on the weight part of the sulfamic acid.

Preferably, when the cosolvent is choline chloride and glycerol, the choline chloride is 4-12 parts by weight and the glycerol is more than 0 and less than or equal to 8 parts by weight based on the weight part of the sulfamic acid.

The invention provides a preparation method of the liquid sulfonating agent in the scheme, which comprises the following steps:

heating urea and a cosolvent to 20-50 ℃, and stirring until the urea and the cosolvent are completely liquid; and mixing the liquid with sulfamic acid at the temperature of 20-50 ℃ to obtain the liquid sulfonating agent.

The invention provides an application of the liquid sulfonating agent in the scheme or the liquid sulfonating agent prepared by the preparation method in the scheme in preparation of a fatliquor through sulfonation reaction.

Preferably, the method for preparing the fatliquor comprises the following steps:

adding the sulfonated substance into a reaction kettle, heating to 90-140 ℃, adding a liquid sulfonating agent, and carrying out sulfonation reaction; and cooling the product system of the sulfonation reaction to 50-70 ℃, adding an emulsifier and water, and emulsifying to obtain the fatting agent.

Preferably, the sulfonated substance is vegetable oil, higher alcohol or fatty alcohol ether; the mass ratio of the sulfonated substance to the liquid sulfonating agent is (28-29): (20-22).

Preferably, the emulsifier is a mixture of fatty amide polyoxyethylene ether and sorbitan monooleate polyoxyethylene ether, and the mass ratio of the sulfonated substance to the emulsifier is (28-29): (1-5).

Preferably, the sulfonation reaction time is 1-5 hours.

The invention provides a liquid sulfonating agent, which is prepared from the following raw materials in parts by weight: 5-8 parts of sulfamic acid, 3.5-10.5 parts of urea and 4-20 parts of cosolvent; the cosolvent is choline chloride and/or glycerol. According to the invention, through mixing sulfamic acid, urea and the cosolvent, sulfamic acid can exist in a liquid state at normal temperature, and can be directly used in a liquid state when being used for sulfonation reaction, so that the problem of poor dissolution of sulfamic acid and urea in the traditional solid-liquid reaction is avoided, and the sulfonation reaction is more uniform and more thorough in modification. In addition, when the liquid sulfonating agent is used for preparing the methyl ester agent through sulfonation reaction, an organic solvent is not required to be added, and the environment-friendly effect is achieved.

Detailed Description

The invention provides a liquid sulfonating agent, which is prepared from the following raw materials in parts by weight: 5-8 parts of sulfamic acid, 3.5-10.5 parts of urea and 4-20 parts of cosolvent; the cosolvent is choline chloride and/or glycerol.

In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.

The liquid sulfonating agent provided by the invention comprises 5-8 parts by weight of sulfamic acid, preferably 6-7 parts by weight. In the present invention, when the liquid sulfonating agent is used for sulfonation, sulfamic acid is used as an effective ingredient.

Based on the weight part of the sulfamic acid, the liquid sulfonating agent provided by the invention comprises 3.5-10.5 parts of urea, preferably 5-9 parts of urea, and more preferably 6-7 parts of urea. In the present invention, urea acts as a catalyst for the sulfonation reaction when the liquid sulfonating agent is used for the sulfonation reaction.

Based on the weight part of the sulfamic acid, the liquid sulfonating agent provided by the invention comprises 4-20 parts of cosolvent, preferably 4-12 parts. In the invention, the cosolvent is choline chloride and/or glycerol. The amount of the cosolvent used is preferably determined according to the kind of the cosolvent used in the present invention.

In the present invention, when the cosolvent is choline chloride, the amount of choline chloride is preferably 4 to 12 parts, more preferably 6 to 10 parts, and even more preferably 7 to 8 parts, based on the weight part of the sulfamic acid. In the invention, choline chloride can form a deep eutectic solvent with urea and sulfamic acid, and is miscible at room temperature. In addition, choline chloride does not react with other raw materials of the sulfonation reaction in the sulfonation reaction to influence the sulfonation reaction.

In the invention, when the cosolvent is glycerol, the glycerol is preferably used in an amount of 4 to 12 parts by weight, more preferably 6 to 10 parts by weight, and even more preferably 7 to 8 parts by weight, based on the parts by weight of the sulfamic acid. The invention utilizes the characteristic that glycerol, urea and sulfamic acid can form solution, so that the sulfonating agent is in liquid state. The invention adopts the technical scheme that the glycerol does not react with other raw materials in the sulfonation reaction to influence the sulfonation reaction, and the synthetic fat liquor obtained by sulfonation plays a role in moistening and moisturizing the leather.

In the invention, when the cosolvent is choline chloride and glycerol, the amount of the choline chloride is preferably 4-12 parts, more preferably 6-10 parts, based on the weight part of the sulfamic acid; the preferable use amount of the glycerol is more than 0 and less than or equal to 8 parts, more preferably 2-6 parts, and further preferably 3-5 parts.

The invention provides a preparation method of the liquid sulfonating agent in the scheme, which comprises the following steps:

heating urea and a cosolvent to 20-50 ℃, and stirring until the urea and the cosolvent are completely liquid; and mixing the liquid with sulfamic acid at the temperature of 20-50 ℃ to obtain the liquid sulfonating agent.

The urea and the cosolvent are heated to 20-50 ℃ and stirred until the urea and the cosolvent are completely liquid.

In the invention, when the cosolvent is choline chloride, the formed liquid is a deep eutectic solvent; when the co-solvent is glycerol, a common solution is formed.

When the cosolvent is choline chloride and glycerol, the choline chloride and the urea are preferably added into a reactor, heated to 20-50 ℃, and stirred until the choline chloride and the urea are completely melted to form a deep eutectic solvent; and mixing the deep eutectic solvent and glycerol at 20-50 ℃, and stirring until the deep eutectic solvent and the glycerol are completely mutually soluble to form liquid.

After the liquid is obtained, the liquid is mixed with sulfamic acid at the temperature of 20-50 ℃ to obtain the liquid sulfonating agent. The present invention preferably performs the mixing under stirring conditions until the sulfamic acid is completely dissolved to obtain the liquid sulfonating agent.

The invention provides an application of the liquid sulfonating agent in the scheme or the liquid sulfonating agent prepared by the preparation method in the scheme in preparation of a fatliquor through sulfonation reaction.

In the present invention, the method for preparing a fatliquor preferably comprises the steps of:

adding the sulfonated substance into a reaction kettle, heating to 90-140 ℃, adding a liquid sulfonating agent, and carrying out sulfonation reaction; and cooling the product system of the sulfonation reaction to 50-70 ℃, adding an emulsifier and water, and emulsifying to obtain the fatting agent.

The method comprises the steps of adding a sulfonated substance into a reaction kettle, heating to 90-140 ℃, adding a liquid sulfonating agent, and carrying out sulfonation reaction.

In the present invention, the sulfonated substance is preferably a vegetable oil or fat, a higher alcohol or a fatty alcohol ether.

In the present invention, the vegetable oil and fat preferably includes one or more of castor oil, soybean oil and linseed oil; the higher alcohol preferably comprises C8-C35 straight-chain fatty alcohol or branched-chain fatty alcohol, more preferably C15-C22 straight-chain fatty alcohol, and further preferably C18-C20 straight-chain fatty alcohol; the fatty alcohol ether preferably comprises C8-C18 fatty alcohol polyoxyethylene ether or isomeric alcohol polyoxyethylene ether, and more preferably C15-C18 fatty alcohol polyoxyethylene ether. In the present invention, the ethylene oxide adduct number of the fatty alcohol-polyoxyethylene ether having C15-C18 is preferably 3 EO-10 EO, and more preferably 5 EO-7 EO.

In the invention, the mass ratio of the sulfonated substance to the liquid sulfonating agent is preferably (28-29): (20-22). In the invention, urea in the liquid sulfonating agent is used as a catalyst, sulfamic acid is used as an effective component of the sulfonating agent, and the cosolvent does not participate in the sulfonation reaction.

In the invention, the sulfonation reaction time is preferably 1-5 hours, and more preferably 2-4 hours.

After the sulfonation reaction is finished, cooling a product system of the sulfonation reaction to 50-70 ℃, adding an emulsifier and water, and emulsifying to obtain the fatliquor.

In the invention, the emulsifier is preferably a mixture of fatty amide polyoxyethylene ether and sorbitan monooleate polyoxyethylene ether, and the mass ratio of the fatty amide polyoxyethylene ether to the sorbitan monooleate polyoxyethylene ether is preferably 1: 1. In the invention, the mass ratio of the sulfonated substance to the emulsifier is preferably (28-29): (1-5), more preferably (28-29): (2-4).

In the present invention, the water is preferably distilled water. The mass ratio of the sulfonated substance to water is preferably (28-29): (80-120), more preferably (28-29): (90-100).

In the present invention, the time for the emulsification is preferably 1 hour. The emulsification is preferably carried out under stirring conditions, which are not particularly required in the present invention and are well known in the art.

The fatting agent prepared by the invention has excellent waterproof performance, flexibility and compatibility, and is environment-friendly because no organic solvent is added.

The liquid sulfonating agent provided by the present invention, its preparation method and application are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

Adding 8 parts by weight of glycerol and 7 parts by weight of urea into a reactor, heating to 40 ℃, and stirring until the urea is completely dissolved in the glycerol to form a first solvent; and mixing the first solvent and 6.8 parts of sulfamic acid at 40 ℃, and stirring until the sulfamic acid is completely dissolved in the first solvent to obtain the liquid sulfonating agent.

Application example 1

Adding 28.8 parts by weight of C1618 alcohol into a reaction kettle, heating to 100 ℃, adding 21.8 parts by weight of the liquid sulfonating agent in the embodiment 1, sulfonating for 3 hours, cooling to 70 ℃, adding 1 part by weight of fatty amide polyoxyethylene ether and 1 part by weight of sorbitan monooleate polyoxyethylene ether and 100 parts by weight of distilled water, stirring and emulsifying for 1 hour to obtain a sulfonated reactant which is used as a fatting agent.

Example 2

Adding 7 parts by weight of choline chloride and 10 parts by weight of urea into a reactor, heating to 40 ℃, and stirring until the urea and the choline chloride are completely melted to form a first solvent; and mixing the first solvent and 8 parts of sulfamic acid at 50 ℃, and stirring until the sulfamic acid is completely dissolved in the first solvent to obtain the liquid sulfonating agent.

Application example 2

Adding 33 parts by weight of C18-20 fatty alcohol polyoxyethylene ether 3EO into a reaction kettle, heating to 140 ℃, adding 25 parts by weight of sulfonating agent in example 2, sulfonating for 1 hour, cooling to 50 ℃, adding 1.5 parts by weight of fatty amide polyoxyethylene ether and 1.5 parts by weight of sorbitan monooleate polyoxyethylene ether and 120 parts by weight of distilled water, stirring and emulsifying for 1 hour to obtain a sulfonated reactant which is used as a fatting agent.

Example 3

Adding 4 parts by weight of glycerol, 6 parts by weight of choline chloride and 9 parts by weight of urea into a reactor, heating to 30 ℃, and stirring until the urea and the choline chloride are completely dissolved in the glycerol to form a first solvent; and mixing the first solvent and 5 parts of sulfamic acid at 30 ℃, and stirring until the sulfamic acid is completely dissolved in the first solvent to obtain the liquid sulfonating agent.

Application example 3

Adding 330 parts by weight of C20 alcohol into a reaction kettle, heating to 120 ℃, adding 250 parts by weight of sulfonating agent in example 3, sulfonating for 5 hours, cooling to 60 ℃, adding 20 parts by weight of fatty amide polyoxyethylene ether and sorbitan monooleate polyoxyethylene ether and 1000 parts by weight of distilled water, stirring and emulsifying for 1 hour to obtain a sulfonated reactant, wherein the sulfonated reactant is used as a fatting agent.

Comparative application example 1

Adding 28.8 parts of C1618 alcohol and 7 parts of urea into a reaction kettle in parts by weight, heating to 100 ℃, slowly adding 6.8 parts of sulfamic acid while stirring, completing the addition within about 1 hour, carrying out sulfonation reaction for 3 hours, cooling to 70 ℃, adding 1 part of fatty amide polyoxyethylene ether and 1 part of sorbitan monooleate polyoxyethylene ether respectively and 100 parts of distilled water, and stirring and emulsifying for 1 hour to obtain a sulfonated reactant.

And (3) performance testing:

taking three pieces of the same parts of the cowhide wet leather, softening, retanning with chromium, neutralizing, retanning and carrying out conventional process operation, respectively adding the sulfonated reactant and the anionic fatliquoring agent LUTAPOL GLH (Qiheqiao chemical Co., Ltd.) which respectively account for 10% of the weight of the leather in the step of fatliquoring after water drainage, treating the leather in a rotary drum for 1.5 hours at 50 ℃, then adding formic acid with the weight of 1.2% of the weight of the leather for fixation, finally washing the leather with water, carrying out vacuum drying, and testing the performance of the leather, wherein the results are shown in Table 1.

TABLE 1 leather Properties

The softness is tested by a leather softness tester DY-4023, the thickening rate is tested by a leather thickness tester XK-3054, the calculation method is the ratio of the thickness of the leather after greasing to the thickness of the blue wet leather, and the dynamic waterproofing is tested by a Maeser leather dynamic waterproofing tester.

As can be seen from Table 1, when the liquid sulfonating agent of the present invention is used in the sulfonation process, the prepared fatting agent has better effect than the common fatting agent when applied to leather because the sulfonation reaction is more sufficient and the product is more stable.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.