CN115925587B

CN115925587B - Tertiary amine dianion type surfactant and preparation method and application thereof

Info

Publication number: CN115925587B
Application number: CN202210187338.7A
Authority: CN
Inventors: 施来顺; 陈立娜; 马京秋; 季通
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2022-02-28
Filing date: 2022-02-28
Publication date: 2024-07-02
Anticipated expiration: 2042-02-28
Also published as: CN115925587A

Abstract

The invention provides a tertiary amine dianion surfactant and a preparation method and application thereof, and relates to the technical field of fine chemical synthesis. The molecular structural general formula of the tertiary amine dianion surfactant is as follows: c _nH_2n+1N(CH₂CH₂CH₂SO₃M)₂, wherein m=na, K; n=12, 14, 16, 18; c _nH_2n+1 is a straight chain alkyl group. The tertiary amine dianion type surfactant prepared by the invention has better surface activity, and can be used as a foam inhibitor, a middle foam surfactant or an emulsifier; meanwhile, the preparation method of the tertiary amine dianion type surfactant is simple, the raw materials are low in cost, and the production cost is low, so that the tertiary amine dianion type surfactant has good industrial production value.

Description

Tertiary amine dianion type surfactant and preparation method and application thereof

Technical Field

The invention relates to the technical field of fine chemical synthesis, in particular to a tertiary amine dianion type surfactant and a preparation method and application thereof.

Background

The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.

Surfactants are mainly divided into ionic and nonionic surfactants, the former mainly including cationic surfactants, anionic surfactants, zwitterionic surfactants, and the like. The application of the surfactant can cover almost all fine chemical fields, such as biopharmaceuticals, daily chemical industry, agricultural production, wastewater treatment, oilfield chemistry, and the like.

In the prior art, a preparation method (CN 108383758A) related to a sulfonic acid group anion gemini surfactant is disclosed: bisphenol A diglycidyl ether, long-chain fatty alcohol, a sulfonating agent and a Lewis acid catalyst are used as raw materials, and the catalyst is prepared through condensation reaction, sulfonation reaction and hydrolysis reaction. Further research discloses a polyether sulfonate-containing surfactant composition, a preparation method and application (CN 109679622A), wherein the composition comprises a betaine surfactant and an anionic surfactant, the betaine surfactant is shown as a formula (I) in the betaine surfactant, and the anionic surfactant is shown as a formula (II) in the betaine surfactant.

In the prior art, the sulfonate surfactant is mainly synthesized by sulfonation reaction with concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or SO ₃ as a sulfonating reagent, and the inventor finds that the drawbacks are that: the sulfonation reaction temperature is higher, the preparation technology is complex, the process danger is high, and the corrosion to equipment is large. Moreover, studies on surfactants have been mainly conducted on surfactant compositions, and there are few reports on single-composition products.

Disclosure of Invention

Aiming at the defects of few varieties of surfactants, complex preparation technology, high process danger and high corrosion to equipment in the prior art and method, the invention provides a tertiary amine dianion type surfactant, and a preparation method and application thereof; meanwhile, the preparation method is simple, the raw materials are low in cost, the production cost is low, and the value of industrial production is good.

In order to achieve the above object, the technical scheme of the present invention is as follows:

in a first aspect of the present invention, there is provided a compound having the general molecular structural formula E:

C_nH_2n+1N(CH₂CH₂CH2SO₃M)₂，

E (E)

Wherein m=na, K; n=12, 14,16,18; c _nH_2n+1 is a straight chain alkyl group.

Proved by researches, the compound has good foam inhibition and foam middle performance and good surface activity, so that the compound can be used as a surfactant. The tertiary amine dianion type surfactant is actually formed by combining sulfonate and amino hydrophilic groups with proper long-carbon-chain lipophilic groups.

Accordingly, in a second aspect of the present invention there is provided a tertiary amine dianionic surfactant which is or comprises a compound of the first aspect described above.

In a third aspect of the present invention, there is provided a process for the preparation of the compound of the first aspect, comprising the steps of:

S1, mixing and reacting primary aliphatic amine, an alcohol solvent and 1, 3-propane sultone to obtain a reaction intermediate J, wherein the structural general formula of the reaction intermediate J is as follows:

intermediate J: the proportion of C _nH_2n+1N(CH₂CH₂CH₂SO₃H)₂ is set up in the range of,

Wherein n=12, 14,16,18; c _nH_2n+1 is a straight chain alkyl group;

s2, adding an alkaline compound aqueous solution into the reaction intermediate J, and mixing and reacting to obtain the compound E.

In a fourth aspect of the present invention, there is provided a compound prepared by the method of preparation of the third aspect.

In a fifth aspect of the invention there is provided the use of a compound according to the first aspect as a suds suppressor, a mid-suds surfactant or an emulsifier.

The technical scheme has the following beneficial effects:

(a) The technical scheme provides a series of tertiary amine dianion surfactants, and sulfonate and amine hydrophilic groups are combined with proper long carbon chain lipophilic groups to form the tertiary amine dianion surfactants with novel chemical structures.

(B) The raw material for preparing the tertiary amine dianion type surfactant is primary fatty amine, and compared with the sulfonate type surfactant commonly used at present, the raw material is cheap and the production cost is low.

(C) In the prior art, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or SO ₃ are used as sulfonating agents to carry out sulfonation reaction to synthesize the sulfonate surfactant, and the sulfonate surfactant has the advantages of higher sulfonation reaction temperature, complex preparation process technology, high process danger and high corrosion to equipment. The preparation method of the tertiary amine dianion type surfactant has simple process, does not need high-temperature reaction, is easy to control, and has good practical application value.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.

FIG. 1 is an infrared spectrum of the product E1-1 of example 1.

FIG. 2 is a nuclear magnetic resonance spectrum of the product E1-1 of example 1.

FIG. 3 is a mass spectrum of the product E1-1 of example 1.

FIG. 4 is an infrared spectrum of the product E2-1 of example 2.

FIG. 5 is a nuclear magnetic resonance spectrum of the product E2-1 of example 2.

FIG. 6 is a mass spectrum of the product E2-1 of example 2.

FIG. 7 is an infrared spectrum of the product E3-1 of example 3.

FIG. 8 is a nuclear magnetic resonance spectrum of the product E3-1 of example 3.

FIG. 9 is a mass spectrum of the product E3-1 of example 3.

FIG. 10 is an infrared spectrum of the product E4-1 of example 4.

FIG. 11 is a nuclear magnetic resonance spectrum of the product E4-1 of example 4.

FIG. 12 is a mass spectrum of the product E4-1 of example 4, FIG. 12A is a positive ion mode, and FIG. 12B is a negative ion mode.

FIG. 13 is an infrared spectrum of product E4-2 of example 5.

FIG. 14 is a nuclear magnetic resonance spectrum of the product E4-2 of example 5.

FIG. 15 is a mass spectrum of the product E4-2 of example 5.

FIG. 16 is a plot of surface tension versus log concentration for product E1-1 of example 1.

FIG. 17 is a plot of surface tension versus log concentration for product E2-1 of example 2.

FIG. 18 is a plot of surface tension versus log concentration for product E3-1 of example 3.

FIG. 19 is a plot of surface tension versus log concentration for product E4-1 of example 4.

FIG. 20 is a plot of surface tension versus log concentration for product E4-2 of example 5.

Detailed Description

It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. 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 application belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.

As described above, the sulfonate surfactant is synthesized by sulfonation reaction mainly using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or SO ₃ as a sulfonating agent, and has the following disadvantages: the sulfonation reaction temperature is higher, the preparation technology is complex, the process danger is high, and the corrosion to equipment is large. Moreover, studies on surfactants have been mainly conducted on surfactant compositions, and there are few reports on single-composition products.

In view of this, the present invention provides a compound useful as a tertiary amine dianionic surfactant, and in particular, in one exemplary embodiment of the present invention, a compound having the molecular structural formula E:

C_nH_2n+1N(CH₂CH₂CH₂SO₃M)₂，

E (E)

Wherein m=na, K; n=12, 14,16,18; c _nH_2n+1 is a straight chain alkyl group.

A compound having the structure of formula E selected from any one or more of:

E1-1：C₁₂H₂₅N(CH₂CH₂CH₂SO₃Na)₂

E1-2：C₁₂H₂₅N(CH₂CH₂CH₂SO₃K)₂

E2-1：C₁₄H₂₉N(CH₂CH₂CH₂SO₃Na)₂

E2-2：C₁₄H₂₉N(CH₂CH₂CH₂SO₃K)₂

E3-1：C₁₆H₃₃N(CH₂CH₂CH₂SO₃Na)₂

E3-2：C₁₆H₃₃N(CH₂CH₂CH₂SO₃K)₂

E4-1：C₁₈H₃₇N(CH₂CH₂CH₂SO₃Na)₂

E4-2：C₁₈H₃₇N(CH₂CH₂CH₂SO₃K)₂

Accordingly, in yet another embodiment of the present invention, there is provided a tertiary amine dianionic surfactant which is or comprises the above compound.

In still another embodiment of the present invention, there is provided a method for preparing the above compound, comprising the steps of:

Wherein n=12, 14,16,18; c _nH_2n+1 is a straight chain alkyl group;

specifically, the reaction general formula is as follows:

The reaction general formula is as follows:

C_nH_2n+1N(CH₂CH₂CH₂SO₃H)₂+2NaOH→C_nH_2n+1N(CH₂CH₂CH₂SO₃Na)₂+2H₂O

(R2)

C_nH_2n+1N(CH₂CH₂CH₂SC)₃H)₂+2KOH→C_nH_2n+1N(CH₂CH₂CH₂SO₃K)₂+2H₂O

(R3)

C_nH_2n+1N(CH₂CH₂CH₂SO₃H)₂+Na₂CO₃→C_nH_2n+1N(CH₂CH₂CH₂SO₃Na)₂+CO₂+H₂O

(R4)

C_nH_2n+1N(CH₂CH₂CH₂SO₃H)₂+K₂CO₃→C_nH_2n+1N(CH₂CH₂CH₂SO₃K)₂+CO₂+H₂O

(R5)

In one or more embodiments, the mole ratio of the primary aliphatic amine, the alcohol solvent, the 1, 3-propane sultone, the alkaline compound and the water is 1:31-54:2.00-2.08:2.00-2.20:7.00-15.00.

In one or more embodiments, in step S1, the primary fatty amine is selected from any one or more of dodecaprimary amine, tetradecprimary amine, hexadecprimary amine, and octadeprimary amine.

In one or more embodiments, in step S1, the alcoholic solvent is selected from any one or more of isopropanol and ethanol.

In one or more embodiments, in step S1, in the synthesis reaction intermediate J, the reaction temperature is 60 to 80 ℃ and the reaction time is 3 to 5 hours;

In one or more embodiments, in step S2, the basic compound is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

In one or more embodiments, in step S2, the reaction temperature is 60 to 80℃and the reaction time is 0.5 to 1.5 hours.

In one or more embodiments, the step S2 further comprises a step of purifying the product E, the step of purifying comprising: and (3) evaporating the solvent from the product E, and then recrystallizing, separating and purifying to obtain a pure product.

Wherein the organic solvent for recrystallization, separation and purification is selected from methanol, ethyl acetate, petroleum ether and the like.

In a preferred embodiment, the preparation method of the compound specifically comprises the following steps:

(1) Adding primary aliphatic amine into a reactor, adding an alcohol solvent, heating, stirring and dissolving, then adding 1, 3-propane sultone in batches, and stirring and reacting for 3-5 hours at 60-80 ℃ after the addition is finished to obtain a reaction intermediate J;

(2) Preparing an alkaline compound aqueous solution by an alkaline compound and water, adding the alkaline compound aqueous solution into the intermediate J in batches, stirring at 60-80 ℃ for reaction for 0.5-1.5 h after the addition is finished, and mixing for reaction to obtain a product E; and (3) evaporating the solvent from the product E, and then recrystallizing, separating and purifying the product E by an organic solvent for 2-3 times to obtain a pure product.

In still another embodiment of the present invention, there is provided a compound prepared by the above preparation method.

In yet another embodiment of the present invention, there is provided the use of the above-described compounds as suds suppressors, mid-suds surfactants or emulsifiers.

The above-mentioned applications, for example, in the production and transportation of emulsified asphalt for highway construction, the production of foam of emulsified asphalt adversely affects its transportation. As another example, in the field of industrial cleaners, the production of foam affects production, which can lead to spillage of materials, waste of materials and environmental pollution.

In the invention, primary fatty amine is used as a main reaction raw material of the tertiary amine dianion type surfactant, and sulfonate and amine groups are introduced into the molecular structure of the surfactant by adding 1, 3-propane sultone and an alkaline compound in the synthesis process of the tertiary amine dianion type surfactant, so that the foam inhibition and the surface properties are improved.

In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and experimental examples.

Example 1

(1) Preparation of tertiary amine dianionic surfactant (product E1-1):

1) 185.35g of dodecylamine, 2200g of isopropanol, and heating and stirring at 75 ℃ to dissolve the dodecylamine. 249.2g of 1, 3-propane sultone are then added in 4 portions and reacted for 4 hours at 75 ℃. Reaction intermediate J-1 was obtained.

2) 86.0G of sodium hydroxide was dissolved in 172.0g of distilled water to obtain an aqueous sodium hydroxide solution, which was gradually added to the reaction intermediate J-1, and the reaction was stirred in a water bath at 75℃for 1 hour. Thus obtaining the tertiary amine dianion type surfactant product E1-1.

The solvent of the synthesized product E1-1 is distilled off, and then the product is purified for 3 times by adopting methanol as the solvent for recrystallization separation, thus obtaining the pure product. FTIR, NMR and MS analysis was then performed to determine foam inhibition, emulsification, foam properties, and surface tension.

FTIR analysis (see fig. 1): 2920cm ^-1 (peak 1) is an asymmetric telescopic vibration absorption peak of methylene, 2850cm ^-1 (peak 2) is a symmetric telescopic vibration absorption peak of methylene, 1469cm ^-1 (peak 3) is an asymmetric bending vibration of methylene, 1186cm ^-1 (peak 4) is a symmetric telescopic vibration absorption peak of sulfonic acid group s=o, 1066cm ^-1 (peak 5) is an asymmetric telescopic vibration absorption peak of sulfonic acid group s=o, 887cm ^-1 (peak 6) is an external bending vibration absorption peak of methylene base surface, 721cm ^-1 (peak 7) is an internal rocking vibration of methylene base surface, and 615cm ^-1 (peak 8) is an telescopic vibration absorption peak of S-O.

¹ H-NMR analysis (see FIG. 2)：¹H NMR(400MHz,DMSO-d₆),δ：0.8351-0.8670(3H,t,J＝6.38Hz,-CH₃),1.2381(18H,s,CH₃(CH₂)₉CH₂CH₂-),1.6132-1.6480(2H,t,CH₃(CH₂)₉CH₂CH₂-),2.2945-2.3651(8H,t,-CH₂CH₂CH₂SO₃Na and-CH₂CH₂CH₂SO₃Na),2.5626-2.6246(2H,t,CH₃(CH₂)₉CH₂CH₂-),3.2991-3.3851(4H,t,-CH₂CH₂CH₂SO₃Na)ppm.

Mass spectrometry (see figure) 3)：HRMS(ESI)(Negative)m/z：[M-2Na⁺+H⁺]^-Calcd for C₁₈H₃₈NO₆S₂,428.2141;Found428.2084.

HRMS(ESI)(Negative)m/z：[M-Na⁺]^-Calcd for C₁₈H₃₇NO₆S₂Na,450.1960;Found 450.2009.

The reaction equation is as follows:

C₁₂H₂₅N(CH₂CH₂CH₂SO₃H)₂+2NaOH→C₁₂H₂₅N(CH₂CH₂CH₂SO₃Na)₂+2H₂O

(2)

Example 2

(1) Preparation of tertiary amine dianionic surfactant (product E2-1):

1) 213.4g of tetradecylamine, 2200g of isopropanol, and dissolved by heating and stirring at 75℃are added into a reactor. 249.2g of 1, 3-propane sultone are then added in 4 portions and reacted for 4 hours at 75 ℃. Reaction intermediate J-2 was obtained.

2) 86.0G of sodium hydroxide was dissolved in 172.0g of distilled water to obtain an aqueous sodium hydroxide solution, which was gradually added to the reaction intermediate J-2, and the reaction was stirred in a water bath at 75℃for 1 hour. Thus obtaining the tertiary amine dianion type surfactant product E2-1.

The solvent of the synthesized product E2-1 is distilled off, and then the product is purified for 3 times by adopting methanol as the solvent for recrystallization separation, thus obtaining the pure product. FTIR, NMR and MS analysis was then performed to determine foam inhibition, emulsification, foam properties, and surface tension.

FTIR analysis (see fig. 4): 2920cm ^-1 (peak 1) is an asymmetric telescopic vibration absorption peak of methylene, 2850cm ^-1 (peak 2) is a symmetric telescopic vibration absorption peak of methylene, 1469cm ^-1 (peak 3) is an asymmetric bending vibration of methylene, 1186cm ^-1 (peak 4) is a symmetric telescopic vibration absorption peak of sulfonic acid group s=o, 1066cm ^-1 (peak 5) is an asymmetric telescopic vibration absorption peak of sulfonic acid group s=o, 894cm ^-1 (peak 6) is an external bending vibration absorption peak of methylene base surface, 721cm ^-1 (peak 7) is an internal rocking vibration of methylene base surface, and 615cm ^-1 (peak 8) is an telescopic vibration absorption peak of S-O.

¹ H-NMR analysis (see FIG. 5)：¹H NMR(400MHz,DMSO-d₆),δ：0.8337-0.8677(3H,t,J＝6.80Hz,-CH₃),1.2348(22H,s,CH₃(CH₂)₁₁CH₂CH₂-),1.6085-1.6457(2H,t,CH₃(CH₂)₁₁CH₂CH₂-),2.3276-2.3608(8H,t,-CH₂CH₂CH₂SO₃Na and-CH₂CH₂CH₂SO₃Na),2.5379-2.5725(2H,t,CH₃(CH₂)₁₁CH₂CH₂-),3.2843-3.3522(4H,t,-CH₂CH₂CH₂SO₃Na)ppm.

Mass spectrometry (see figure) 6)：HRMS(ESI)(Negative)m/z：[M-2Na⁺+H⁺]^-Calcd for C₂₀H₄₂NO₆S₂,456.2454;Found 456.2288.

The reaction equation is as follows:

C₁₄H₂₉N(CH₂CH₂CH₂SO₃H)₂+2NaOH→C₁₄H₂₉N(CH₂CH₂CH₂SO₃Na)₂+2H₂O

(4)

Example 3

(1) Preparation of tertiary amine dianionic surfactant (product E3-1):

1) 241.46g of hexadecylamine, 2200g of isopropanol, and heating and stirring at 75 ℃ to dissolve the hexadecylamine. 249.2g of 1, 3-propane sultone are then added in 4 portions and reacted for 4 hours at 75 ℃. Reaction intermediate J-3 was obtained.

2) 86.0G of sodium hydroxide was dissolved in 172.0g of distilled water to obtain an aqueous sodium hydroxide solution, which was gradually added to the reaction intermediate J-3, and the reaction was stirred in a water bath at 75℃for 1 hour. Thus obtaining the tertiary amine dianion type surfactant product E3-1.

The solvent of the synthesized product E3-1 is distilled off, and then the product is purified for 3 times by adopting methanol as the solvent for recrystallization separation, thus obtaining the pure product. FTIR, NMR and MS analysis was then performed to determine foam inhibition, emulsification, foam properties, and surface tension.

FTIR analysis (see fig. 7): 2920cm ^-1 (peak 1) is an asymmetric telescopic vibration absorption peak of methylene, 2850cm ^-1 (peak 2) is a symmetric telescopic vibration absorption peak of methylene, 1469cm ^-1 (peak 3) is an asymmetric bending vibration of methylene, 1186cm ^-1 (peak 4) is a symmetric telescopic vibration absorption peak of sulfonic acid group s=o, 1066cm ^-1 (peak 5) is an asymmetric telescopic vibration absorption peak of sulfonic acid group s=o, 894cm ^-1 (peak 6) is an external bending vibration absorption peak of methylene base surface, 721cm ^-1 (peak 7) is an internal rocking vibration of methylene base surface, and 615cm ^-1 (peak 8) is an telescopic vibration absorption peak of S-O.

¹ H-NMR analysis (see FIG. 8)：¹H NMR(400MHz,DMSO-d₆),δ：0.8342-0.8675(3H,t,J＝6.66Hz,-CH₃),1.2335(26H,s,CH₃(CH₂)₁₃CH₂CH₂-),1.6029-1.6403(2H,t,CH₃(CH₂)₁₃CH₂CH₂-),2.3268-2.3654(8H,t,-CH₂CH₂CH₂SO₃Na and-CH₂CH₂CH₂SO₃Na),2.5778-2.6040(2H,t,CH₃(CH₂)₁₃CH₂CH₂-),3.3135-3.3682(4H,t,-CH₂CH₂CH₂SO₃Na)ppm.

Mass spectrometry (see figure) 9)：HRMS(ESI)(Negative)m/z：[M-2Na⁺+H⁺]^-Calcd for C₂₂H₄₆NO₆S₂,484.2767;Found 484.2505.

HRMS(ESI)(Negative)m/z：[M-2Na⁺]^2-/2Calcd for C₂₂H₄₅NO₆S₂/2,241.6344;Found 241.6468.

The reaction equation is as follows:

C₁₆H₃₃N(CH₂CH₂CH₂SO₃H)₂+2NaOH→C₁₆H₃₃N(CH₂CH₂CH₂SO₃Na)₂+2H₂O

(6)

Example 4

(1) Preparation of tertiary amine dianionic surfactant (product E4-1):

1) 269.51g of octadecyl amine, 2200g of isopropanol, and heating and stirring at 75 ℃ to dissolve the components are added into a reactor. 249.2g of 1, 3-propane sultone are then added in 4 portions and reacted for 4 hours at 75 ℃. Reaction intermediate J-4 was obtained.

2) 86.0G of sodium hydroxide was dissolved in 172.0g of distilled water to obtain an aqueous sodium hydroxide solution, which was gradually added to the reaction intermediate J-4, and the reaction was stirred in a water bath at 75℃for 1 hour. Thus obtaining the tertiary amine dianion type surfactant product E4-1.

The solvent of the synthesized product E4-1 is distilled off, and then the product is purified for 3 times by adopting methanol as the solvent for recrystallization separation, thus obtaining the pure product. FTIR, NMR and MS analysis was then performed to determine foam inhibition, emulsification, foam properties, and surface tension.

FTIR analysis (see fig. 10): 2918cm ^-1 (peak 1) is an asymmetric telescopic vibration absorption peak of methylene, 2850cm ^-1 (peak 2) is a symmetric telescopic vibration absorption peak of methylene, 1469cm ^-1 (peak 3) is an asymmetric bending vibration of methylene, 1186cm ^-1 (peak 4) is a symmetric telescopic vibration absorption peak of sulfonic acid group s=o, 1066cm ^-1 (peak 5) is an asymmetric telescopic vibration absorption peak of sulfonic acid group s=o, 894cm ^-1 (peak 6) is an external bending vibration absorption peak of methylene base surface, 725cm ^-1 (peak 7) is an internal rocking vibration of methylene base surface, and 621cm ^-1 (peak 8) is an telescopic vibration absorption peak of S-O.

¹ H-NMR analysis (see FIG. 11)：¹H NMR(400MHz,DMSO-d₆),δ:0.8346-0.8689(3H,t,J＝6.86Hz,-CH₃),1.2338(30H,s,CH₃(CH₂)₁₅CH₂CH₂-),1.5933-1.6269(2H,t,CH₃(CH₂)₁₅CH₂CH₂-),2.3014-2.3530(8H,t,-CH₂CH₂CH₂SO₃Na and-CH₂CH₂CH₂SO₃Na),2.6404-2.7157(2H,t,CH₃(CH₂)₁₅CH₂CH₂-),3.2951-3.3119(4H,t,-CH₂CH₂CH₂SO₃Na)ppm.

Mass spectrometry (see FIGS. 12A and 12B) 12B)：HRMS(ESI)(Negative)m/z:[M-2Na⁺]^2-/2Calcd for C₂₄H₄₉NO₆S₂/2,255.6501;Found 255.6642.

HRMS(ESI)(Negative)m/z:[M-2Na⁺+H⁺]^-Calcd for C₂₄H₅₀NO₆S₂,512.3080;Found 512.2848.

HRMS(ESI)(Positive)m/z:[M+H⁺]⁺Calcd for C₂₄H₅₀NO₆S₂Na₂,558.2875;Found 558.2899.

The reaction equation is as follows:

C₁₈H₃₇N(CH₂CH₂CH₂SO₃H)₂+2NaOH→C₁₈H₃₇N(CH₂CH₂CH₂SO₃Na)₂+2H₂O

(8)

Example 5

(1) Preparation of tertiary amine dianionic surfactant (product E4-2):

2) 120.6G of potassium hydroxide was dissolved in 240.0g of distilled water to obtain an aqueous potassium hydroxide solution, which was gradually added to the reaction intermediate J-4, and reacted in a water bath at 75℃with stirring for 1 hour. Thus obtaining the tertiary amine dianion type surfactant product E4-2.

The solvent of the synthesized product E4-2 is distilled off, and then the product is purified for 3 times by adopting methanol as the solvent for recrystallization separation, thus obtaining the pure product. FTIR, NMR and MS analysis was then performed to determine foam inhibition, emulsification, foam properties, and surface tension.

FTIR analysis (see fig. 13): 2920cm ^-1 (peak 1) is an asymmetric telescopic vibration absorption peak of methylene, 2850cm ^-1 (peak 2) is a symmetric telescopic vibration absorption peak of methylene, 1469cm ^-1 (peak 3) is an asymmetric bending vibration of methylene, 1188cm ^-1 (peak 4) is a symmetric telescopic vibration absorption peak of sulfonic acid group s=o, 1060cm ^-1 (peak 5) is an asymmetric telescopic vibration absorption peak of sulfonic acid group s=o, 889cm ^-1 (peak 6) is an external bending vibration absorption peak of methylene base surface, 721cm ^-1 (peak 7) is an internal rocking vibration of methylene base surface, 619cm ^-1 (peak 8) is an telescopic vibration absorption peak of S-O.

¹ H-NMR analysis (see FIG. 14)：¹H NMR(400MHz,DMSO-d₆),δ：0.8363-0.8704(3H,t,J＝6.82Hz,-CH₃),1.2361(30H,s,CH₃(CH₂)₁₅CH₂CH₂-),1.6020-1.6394(2H,t,CH₃(CH₂)₁₅CH₂CH₂-),2.3174-2.3535(8H,t,-CH₂CH₂CH₂SO₃K and-CH₂CH₂CH₂SO₃K),2.5471-2.5815(2H,t,CH₃(CH₂)₁₅CH₂CH₂-),3.2661-3.2835(4H,t,-CH₂CH₂CH₂SO₃K)ppm.

Mass spectrometry (see figure) 15)：HRMS(ESI)(Negative)m/z：[M-2K⁺+H⁺+CH₃OH]^-Calcd for C₂₅H₅₄NO₇S₂,544.3342;Found544.3657.

HRMS(ESI)(Negative)m/z：[M-2K⁺+H⁺]^-Calcd for C₂₄H₅₀NO₆S₂,512.3080;Found512.3379.

HRMS(ESI)(Negative)m/z：[M-2K⁺]^2-/2Calcd for C₂₄H₄₉NO₆S₂/2,255.6501;Found 255.6856.

The reaction equation is as follows:

C₁₈H₃₇N(CH₂CH₂CH₂SO₃H)₂+2KOH→C₁₈H₃₇N(CH₂CH₂CH₂SO₃K)₂+2H₂O

(9)

Experimental example 1

The experimental examples carried out foam inhibition performance experiments on tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1to 5, and the foam inhibition performance after purification was measured respectively.

The method comprises the following steps: 10 ml of 0.5% (mass fraction) aqueous sodium dodecyl benzene sulfonate (LBS) and a certain amount of sample were poured into a 100 ml stoppered cylinder at room temperature, the stoppered was plugged, and the total foam volume V ₁ recorded immediately after 20 vigorous shaking. The foam suppression value T is calculated, and the size of the foam suppression value T represents the foam suppression capacity of the product.

T＝(V₀-V₁)/V₀

Wherein V ₀ is the total volume of foam immediately after shaking in a blank test, and ml; v ₁ is the total foam volume immediately after shaking when the sample was added, ml.

Results: the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 were compared with OP-10 (commercial products), and the foam suppression properties are shown in Table 1.

TABLE 1 foam inhibition Properties of purified samples and OP-10 (commercial products)

Conclusion: the tertiary amine dianion type surfactant E4-2 prepared in the example 5 has better foam inhibition capability after purification.

Experimental example 2

The experimental examples were conducted to determine the emulsifying ability of the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5.

The method comprises the following steps: at room temperature, 20 ml of a sample aqueous solution with mass fraction of 0.1% and an aqueous solution of OP-10 (commercial product) and 20 ml of liquid paraffin were poured into a 100 ml cylinder with a stopper, the stopper was plugged, left to stand for 1 minute after 5 times of vigorous shaking, and after 5 times of repetition, the time for separating out 10ml of water was recorded.

Results: the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 were compared with OP-10 (commercial products), and the emulsifying capacity was shown in Table 2.

TABLE 2 emulsifying capacity

Product(s)	Time to split(s)
		Example 1 product E1-1	266
Example 2 product E2-1	334
		Example 3 product E3-1	387
Example 4 product E4-1	485
		Example 5 product E4-2	812
OP-10	684

Conclusion: the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 all have good emulsifying capacity. And, the emulsifying capacity of the product E4-2 of example 5 is better than OP-10.

Experimental example 3

The foaming property and foam stability of the purified samples were measured for the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5.

The method comprises the following steps: 80 ml of the aqueous solution of the purified sample was prepared at a concentration of 0.001mol/L for use. 20ml of the prepared solution is placed in a 100 ml cylinder with a plug, and the temperature is kept for 10 minutes in a water bath kettle at 25 ℃. Shaking the above solution for 20 times, standing in water bath, and recording initial volume of foam (G ₀); after 5 minutes the volume of foam (G ₅) was recorded; the foam volume decays half the time of the initial volume (t _1/2, half-life). Repeat 3 times and take the average.

Results: the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 were compared with sodium dodecylbenzenesulfonate, as shown in Table 3.

TABLE 3 foamability and foam stability

Conclusion: compared with sodium dodecyl benzene sulfonate, the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 have slightly lower foamability and better foam stability after purification. The tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 are described as being medium foaming surfactants.

Experimental example 4

The surface tension of the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 was measured, and the surface tension and Critical Micelle Concentration (CMC) of the purified products were measured.

The method comprises the following steps: a JHZL type full-automatic surface tension meter (manufactured by Yangzhou Jun electric Co., ltd.) is selected for measurement, a series of tertiary amine dianion type surfactant E1-E4-2 aqueous solutions with different concentrations are prepared, the surface tension is measured by a hanging ring method, and a surface tension-log curve is drawn to obtain CMC and the surface tension (gamma _CMC) under the CMC.

Results: the surface tension versus concentration log graphs of the tertiary amine dianion surfactants E1-1 to E4-2 prepared in examples 1 to 5 are shown in FIGS. 16 to 20. As can be seen, in example 1, the CMC of the product E1-1 was 2.65X10 ^-4 mol/L, and the surface tension (. Gamma. _CMC) at CMC was 48.5mN/m.

In example 2, the CMC of the product E2-1 was 7.02X10 ^-5 mol/L and the surface tension (. Gamma. _CMC) at CMC was 39.0mN/m.

In example 3, the CMC of the product E3-1 was 1.64X10 ^-4 mol/L and the surface tension (. Gamma. _CMC) at CMC was 46.8mN/m.

In example 4, the CMC of the product E4-1 was 2.76X10 ^-4 mol/L and the surface tension (. Gamma. _CMC) at CMC was 45.5mN/m.

In example 5, the CMC of the product E4-2 was 3.02X10 ^-4 mol/L and the surface tension (. Gamma. _CMC) at CMC was 45.0mN/m.

The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The application of a compound as a foam inhibitor, a middle foam surfactant or an emulsifier is characterized in that the molecular structural formula E of the compound is as follows:

C_nH_2n+1N(CH₂CH₂CH₂SO₃M)₂，

E (E)

Wherein m=k; n=18; c _nH_2n+1 is a straight chain alkyl group.

2. Use of a compound according to claim 1, wherein the method of preparing the compound comprises the steps of:

Wherein n=18; c _nH_2n+1 is a straight chain alkyl group;

The primary fatty amine is octadecylamine;

3. The use of the compound according to claim 2, wherein the molar ratio of the primary aliphatic amine, the alcohol solvent, the 1, 3-propane sultone, the basic compound and the water is 1:31-54:2.00-2.08:2.00-2.20:7.00-15.00.

4. The use of a compound according to claim 2, wherein in step S1,

The alcohol solvent is selected from any one or more of isopropanol and ethanol;

In the synthesis reaction intermediate J, the reaction temperature is 60-80 ℃ and the reaction time is 3-5 h.

5. The use of a compound according to claim 2, wherein in step S2, the basic compound is selected from any one or more of potassium hydroxide and potassium carbonate;

the reaction temperature is 60-80 ℃ and the reaction time is 0.5-1.5 h.

6. The use of a compound according to claim 2, wherein step S2 further comprises a step of purifying product E, said step of purifying comprising: and (3) evaporating the solvent from the product E, and then recrystallizing, separating and purifying to obtain a pure product.

7. The use of a compound according to claim 6, wherein the organic solvent separated and purified by recrystallization is selected from the group consisting of methanol, ethyl acetate and petroleum ether.

8. The use of a compound according to claim 2, comprising in particular the steps of: