Chlorine-free organic counterion quaternary ammonium salt gemini surfactant, its preparation method and application

Abstract

The application belongs to the technical field of surfactants, and discloses a kind of organic counterion quaternary ammonium salt gemini surfactants without chlorine and a preparation method and application thereof.The organic counterion quaternary ammonium salt gemini surfactants without chlorine are obtained by adding a certain amount of alkyl diamine compound acidified by organic acid into C1-C 18 The alkyl glycidyl ether is subjected to quaternary ammonium reaction by adding a certain amount of alkyl diamine compound acidified by organic acid.The obtained organic counterion quaternary ammonium salt gemini surfactants without chlorine contain two organic counterions and two hydroxyl groups, the synthesis process is simple, the conditions are mild, and no toxic and harmful by-products are produced, which can avoid the corrosion of halogen ions to equipment and environmental pollution during preparation.

Description

Technical Field

[0001] This invention relates to the field of surfactant technology, and in particular to a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, its preparation method, and its application. Background Technology

[0002] Gemini surfactants can be viewed as two single-chain surfactants linked by a spacer group. Compared to ordinary single-chain surfactants, gemini surfactants have two tail chains, exhibiting a stronger hydrophobic effect. Furthermore, the spacer group connecting the hydrophilic head groups effectively reduces electrostatic repulsion, resulting in gemini surfactants with lower Krafft points, lower CMC, higher interfacial adsorption tendency, easier aggregation, and unique rheological properties. Gemini surfactants can be classified into cationic, anionic, nonionic, and amphoteric types based on the charge of their head groups. Quaternary ammonium salt gemini surfactants are the most widely studied, primarily being nitrogen-containing organic amine derivatives. These quaternary ammonium salt gemini surfactants are widely used in disinfection, petroleum extraction, and dyeing auxiliaries.

[0003] Traditional quaternary ammonium salt-type gemini surfactants are typically synthesized from tertiary amines and toxic, corrosive quaternizing agents such as haloalkanes via a quaternization reaction, posing certain environmental pollution problems. Furthermore, the counterion type of common quaternary ammonium salt-type gemini surfactants is primarily a halide counterion (Cl-). - ,Br - and I - The limited availability of these technologies has restricted the development of quaternary ammonium salt-type gemini surfactants. To meet diverse needs, researchers have synthesized quaternary ammonium salt-type gemini surfactants with different functionalities by designing different structures. However, these studies often focus on improving the hydrophobic hydrocarbon group or hydrophilic head group, resulting in a limited variety of products that are difficult to meet market demands.

[0004] Counterions, as a crucial component of quaternary ammonium gemini surfactants, influence the interfacial adsorption, micellar aggregation behavior, and application performance of surfactants. Replacing traditional halide counterions with organic counterions to prepare novel quaternary ammonium gemini surfactants can not only improve product properties but also reduce equipment corrosion and enrich the variety of quaternary ammonium gemini surfactants. Furthermore, the introduction of organic counterions is expected to further enhance the potential of quaternary ammonium gemini surfactants in applications such as sterilization, disinfection, and metal corrosion inhibition.

[0005] Therefore, there is an urgent need in this field to design a new quaternary ammonium salt gemini surfactant containing organic counterions, which can not only ensure a novel structure and enrich the variety of quaternary ammonium salt gemini surfactants, but also ensure that the surfactant synthesis method is simple, the process conditions are mild, the synthesis process does not corrode equipment, and does not produce toxic or harmful byproducts, thus meeting the needs of economic and environmental protection and the requirements of green chemistry. Summary of the Invention

[0006] The purpose of this invention is to provide a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, its preparation method, and its application, in order to solve the problems of corrosion hazards to equipment and environmental pollution caused by halogen ions during the preparation of traditional halogen-containing counterionic quaternary ammonium salt cationic gemini surfactants.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] This invention provides a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, the structural formula of which is:

[0009]

[0010] Where R is C1 to C 18 Alkyl group; n is any integer from 2 to 10; X is a monobasic organic acid anion.

[0011] The present invention also provides a method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, comprising the following steps:

[0012] (1) After mixing alkyl diamine compounds, organic acids and solvents, a protonated intermediate compound is obtained by reaction;

[0013] (2) After mixing the protonation intermediate compound, alkyl glycidyl ether and solvent, the reaction yields a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant.

[0014] Preferably, the structural formula of the alkyl diamine compound is: Wherein, n is any integer from 2 to 10; the organic acid is a monoprotic organic acid; the structural formula of the alkyl glycidyl ether is: Where R is C1 to C 18 Alkyl groups; the solvents in steps (1) and (2) are independently C1 to C4 low alcohols.

[0015] Preferably, the molar ratio of the alkyl diamine compound to the organic acid is 1:2 to 2.2; and the molar ratio of the alkyl diamine compound to the alkyl glycidyl ether is 1:2 to 2.4.

[0016] Preferably, the total mass of the solvent in steps (1) and (2) is 30-50% of the total mass of the solvent, organic acid and alkyl glycidyl ether.

[0017] Preferably, the mass ratio of the solvent in step (1) to the solvent in step (2) is 1-2:1-4.

[0018] Preferably, in step (1), the specific mixing step is as follows: the organic acid and solvent are mixed and then added dropwise to the alkyl diamine compound.

[0019] Preferably, in step (1), the reaction time is 0.5 to 2 hours.

[0020] Preferably, in step (2), the reaction temperature is 80-120°C and the reaction time is 4-12 hours.

[0021] The present invention also provides the application of the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant in disinfection, petroleum extraction and printing and dyeing.

[0022] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] 1. The chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant provided by this invention contains two organic counterions and two hydroxyl groups. It is a structurally stable organic compound with a novel molecular structure, which can enrich the diversity of quaternary ammonium salt-type cationic gemini surfactants.

[0024] 2. The preparation process of the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant described in this invention is simple, the reaction raw materials are readily available, the reaction conditions are mild, and the entire reaction process is green and environmentally friendly. It does not use corrosive haloalkane reagents that are prone to causing environmental pollution, avoids the corrosion of equipment by halogen elements, and also effectively reduces the toxicity and irritation of the product. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0026] Figure 1 The NMR spectra of the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactants obtained in Examples 1 and 2 are shown. In the NMR spectrum, b = 9 corresponds to the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained in Example 1, and b = 11 corresponds to the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained in Example 2.

[0027] Figure 2 The NMR spectra of the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactants obtained in Examples 3 and 4 are shown. In the NMR spectrum, b = 9 corresponds to the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained in Example 3, and b = 11 corresponds to the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained in Example 4.

[0028] Figure 3 The NMR spectra of the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactants obtained in Examples 5 and 6 are shown. In the NMR spectrum, b = 9 corresponds to the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained in Example 5, and b = 11 corresponds to the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained in Example 6. Detailed Implementation

[0029] This invention provides a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, the structural formula of which is:

[0030]

[0031] Wherein, R is preferably C1 to C 18 Alkyl groups, more preferably C2-C3 16 The alkyl group; n is preferably any integer from 2 to 10, more preferably any integer from 3 to 8; X is preferably a monobasic organic acid group, more preferably formate, methanesulfonate or benzenesulfonate.

[0032] The present invention also provides a method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, comprising the following steps:

[0033] (1) After mixing alkyl diamine compounds, organic acids and solvents, a protonated intermediate compound is obtained by reaction;

[0034] (2) After mixing the protonation intermediate compound, alkyl glycidyl ether and solvent, the reaction yields a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant.

[0035] In this invention, the preferred structural formula of the alkyl diamine compound is: Wherein, n is preferably any integer from 2 to 10, more preferably any integer from 3 to 8; the organic acid is preferably a monoprotic organic acid, more preferably formic acid, acetic acid, propionic acid, butyric acid, lactic acid, methanesulfonic acid, benzenesulfonic acid, or p-toluenesulfonic acid; the structural formula of the alkyl glycidyl ether is preferably: Wherein, R is preferably C1 to C 18 Alkyl groups, more preferably C2-C3 16Alkyl groups; the solvents in steps (1) and (2) are preferably low-carbon alcohols of C1 to C4, and more preferably low-carbon alcohols of C2 to C3.

[0036] In this invention, the molar ratio of the alkyl diamine compound to the organic acid is preferably 1:2 to 2.2, more preferably 1:2.1 to 2.2; the molar ratio of the alkyl diamine compound to the alkyl glycidyl ether is preferably 1:2 to 2.4, more preferably 1:2.2 to 2.3.

[0037] The total mass of the solvent in steps (1) and (2) of the present invention is preferably 30-50% of the total mass of the solvent, organic acid and alkyl glycidyl ether, and more preferably 40-50%.

[0038] The mass ratio of the solvent in step (1) to the solvent in step (2) of the present invention is preferably 1-2:1-4, and more preferably 1.2-1.8:2-3.

[0039] In step (1) of the present invention, the specific mixing step is as follows: the organic acid and solvent are mixed and then added dropwise to the alkyl diamine compound; the dropwise addition rate is preferably 3 to 5 s / drop, and more preferably 4 s / drop.

[0040] In step (1) of the present invention, the reaction time is preferably 0.5 to 2 hours, and more preferably 1 to 1.5 hours.

[0041] In step (1) of this invention, the reaction ends when the free amine content in the reaction vessel is less than 2%.

[0042] In step (2) of the present invention, the specific steps for mixing the protonation intermediate compound, alkyl glycidyl ether and solvent are as follows: after the acid mist in the reaction vessel containing the protonation intermediate compound disappears, alkyl glycidyl ether and solvent are added.

[0043] In step (2) of the present invention, the reaction temperature is preferably 80-120°C, more preferably 90-110°C; the reaction time is preferably 4-12h, more preferably 6-10h.

[0044] In step (2) of the present invention, the reaction is carried out under stirring conditions, and the stirring speed is preferably 800-1000 r / min, more preferably 900-950 r / min.

[0045] In step (2) of the present invention, after the reaction is completed, the obtained product is sequentially subjected to vacuum distillation, recrystallization and drying to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant.

[0046] The purpose of the vacuum distillation is to remove the solvent from the resulting product;

[0047] The reagent used for recrystallization is ethyl acetate or methanol;

[0048] The drying temperature is preferably 60-80℃, more preferably 70-75℃; the drying time is preferably 0.5-1h, more preferably 40-50min.

[0049] The present invention also provides the application of the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant in disinfection, petroleum extraction and printing and dyeing.

[0050] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0051] Example 1

[0052] The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant described in this embodiment includes the following steps:

[0053] S1. Take 8.6 g (0.05 mol) of N,N,N',N'-1,6-tetramethylhexanediamine (n=6) into a four-necked flask. While stirring, add a solution of formic acid in n-propanol (5.44 g of n-propanol, 4.60 g of formic acid, 0.1 mol) at a rate of 3 s / drop. The stirring speed is 800 r / min. During the addition, heat will be released and acid mist will be generated. After 0.5 h of reaction, the free amine content is measured to be 0.2%, and the reaction is terminated.

[0054] S2. After the acid mist generated in the reaction in S1 disappears, add dodecyl glycidyl ether (R is C). 12 A solution of n-propanol (10.89 g of n-propanol, 24.9 g of dodecyl glycidyl ether, 0.1 mol) was reacted at 90 °C for 6 h with a stirring speed of 800 r / min to obtain a clear, yellow product. The product was then subjected to vacuum distillation to remove the solvent, recrystallized with ethyl acetate, and dried at 80 °C for 40 min to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant with a yield of 92.1%.

[0055] Example 2

[0056] The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant described in this embodiment includes the following steps:

[0057] S1. Take 5.68 g (0.033 mol) of N,N,N',N'-1,6-tetramethylhexanediamine (n=6) into a four-necked flask. While stirring, add a solution of formic acid in n-propanol (8.99 g of n-propanol, 3.34 g of formic acid, 0.0726 mol) at a rate of 3 s / drop. The stirring speed is 950 r / min. During the addition, heat will be released and acid mist will be generated. After 0.5 h of reaction, the free amine content is measured to be 0.2%, and the reaction is terminated.

[0058] S2. After the acid mist generated in the reaction in S1 disappears, add tetradecyl glycidyl ether (R is C). 14 A solution of n-propanol (19.77 g of n-propanol, 19.72 g of tetradecyl glycidyl ether, 0.0729 mol) was reacted at 90 °C for 10 h with a stirring speed of 800 r / min to obtain a clear, yellow product. The solvent was removed by vacuum distillation, and the product was recrystallized with ethyl acetate and dried at 80 °C for 40 min to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant with a yield of 95.6%.

[0059] Example 3

[0060] The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant described in this embodiment includes the following steps:

[0061] S1. Take 8.6 g (0.05 mol) of N,N,N',N'-1,6-tetramethylhexanediamine (n=6) into a four-necked flask. While stirring, add a solution of methanesulfonic acid in n-propanol (12.07 g of n-propanol, 10.57 g of methanesulfonic acid, 0.11 mol) at a rate of 3 s / drop. The stirring speed is 800 r / min. During the addition, heat will be released and acid mist will be generated. After reacting for 1 hour, the free amine content is measured to be 0.3%, and the reaction is terminated.

[0062] S2. After the acid mist generated in the reaction in S1 disappears, add dodecyl glycidyl ether (R is C). 12 A solution of n-propanol (25.19 g of n-propanol, 29.09 g of dodecyl glycidyl ether, 0.12 mol) was reacted at 90 °C for 6 h with a stirring speed of 800 r / min to obtain a clear, yellow product. The product was then subjected to vacuum distillation to remove the solvent, recrystallized with ethanol, and dried at 80 °C for 40 min to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant with a yield of 90.7%.

[0063] Example 4

[0064] The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant described in this embodiment includes the following steps:

[0065] S1. Take 6g (0.0344mol) of N,N,N',N'-1,6-tetramethylhexanediamine (n=6) into a four-necked flask. While stirring, add a solution of methanesulfonic acid in n-propanol (10g of n-propanol, 6.81g of methanesulfonic acid, 0.0709mol) at a rate of 3s / drop. The stirring speed is 900r / min. During the addition process, heat will be released and acid mist will be generated. After reacting for 1 hour, the free amine content is measured to be 0.3%, and the reaction is terminated.

[0066] S2. After the acid mist generated in the reaction in S1 disappears, add tetradecyl glycidyl ether (R is C). 14 A solution of n-propanol (11.1 g n-propanol, 18.84 g tetradecyl glycidyl ether, 0.0697 mol) was reacted at 90 °C for 10 h with a stirring speed of 800 r / min to obtain a clear, yellow product. The solvent was removed by vacuum distillation, the product was recrystallized with ethanol, and dried at 80 °C for 40 min to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant with a yield of 96.5%.

[0067] Example 5

[0068] The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant described in this embodiment includes the following steps:

[0069] S1. Take 8.6 g (0.05 mol) of N,N,N',N'-1,6-tetramethylhexanediamine (n=6) into a four-necked flask. While stirring, add a solution of benzenesulfonic acid in n-propanol (10.97 g of n-propanol, 17.08 g of benzenesulfonic acid, 0.108 mol) at a rate of 3 s / drop. The stirring speed is 1000 r / min. During the addition, heat will be released and acid mist will be generated. After 1.5 h of reaction, the free amine content is measured to be 0.4%, and the reaction is terminated.

[0070] S2. After the acid mist generated in the reaction in S1 disappears, add dodecyl glycidyl ether (R is C). 12 A solution of n-propanol (18.28 g n-propanol, 28.64 g dodecyl glycidyl ether, 0.118 mol) was reacted at 90 °C for 6 h with a stirring speed of 800 r / min to obtain a clear, yellow product. The product was then subjected to vacuum distillation to remove the solvent, recrystallized with ethyl acetate, and dried at 80 °C for 40 min to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant with a yield of 93.5%.

[0071] Example 6

[0072] The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant described in this embodiment includes the following steps:

[0073] S1. Take 4.47 g (0.026 mol) of N,N,N',N'-1,6-tetramethylhexanediamine (n=6) into a four-necked flask. While stirring, add a solution of benzenesulfonic acid in n-propanol (7.27 g of n-propanol, 9.05 g of benzenesulfonic acid, 0.0572 mol) at a rate of 3 s / drop. The stirring speed is 900 r / min. During the addition, heat will be released and acid mist will be generated. After 1.5 h of reaction, the free amine content is measured to be 0.4%, and the reaction is terminated.

[0074] S2. After the acid mist generated in the reaction in S1 disappears, add tetradecyl glycidyl ether (R is C). 14 A solution of n-propanol (8.54 g n-propanol, 12.1 g tetradecyl glycidyl ether, 0.0574 mol) was reacted at 90 °C for 10 h with a stirring speed of 800 r / min to obtain a clear, yellow product. The product was then subjected to vacuum distillation to remove the solvent, recrystallized with ethyl acetate, and dried at 80 °C for 40 min to obtain a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant with a yield of 97.4%.

[0075] Depend on Figures 1-3 As can be seen from Examples 1 to 6, the chlorine-free organic counterionic quaternary ammonium salt-type gemini surfactant obtained by the present invention has a high yield (90.7-97.4%), a simple preparation process, readily available raw materials, and is halogen-free, thus avoiding the corrosion of equipment and environmental pollution caused by halogen ions, meeting the needs of economic and environmental protection and the requirements of green chemistry.

[0076] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A chlorine-free organic counterionic quaternary ammonium salt gemini surfactant, characterized in that, The structural formula of the organic counterionic quaternary ammonium salt gemini surfactant is: Where R is C1 to C 18 Alkyl group; n is any integer from 2 to 10; X is a monobasic organic acid anion.

2. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 1, characterized in that, Includes the following steps: (1) After mixing alkyl diamine compounds, organic acids and solvents, a protonated intermediate compound is obtained by reaction; (2) After mixing the protonation intermediate compound, alkyl glycidyl ether and solvent, the reaction yields a chlorine-free organic counterionic quaternary ammonium salt gemini surfactant.

3. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 2, characterized in that, The structural formula of the alkyldiamine compound is: Wherein, n is any integer from 2 to 10; the organic acid is a monoprotic organic acid; the structural formula of the alkyl glycidyl ether is: Where R is C1 to C 18 Alkyl groups; the solvents in steps (1) and (2) are independently C1 to C4 low alcohols.

4. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 3, characterized in that, The molar ratio of the alkyl diamine compound to the organic acid is 1:2 to 2.2; the molar ratio of the alkyl diamine compound to the alkyl glycidyl ether is 1:2 to 2.

4.

5. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to any one of claims 2 to 4, characterized in that, The total mass of the solvent in steps (1) and (2) is 30-50% of the total mass of the solvent, organic acid, and alkyl glycidyl ether.

6. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 5, characterized in that, The mass ratio of the solvent in step (1) to the solvent in step (2) is 1-2:1-4.

7. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 6, characterized in that, In step (1), the specific steps of mixing are as follows: the organic acid and solvent are mixed and then added dropwise to the alkyl diamine compound.

8. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 7, characterized in that, In step (1), the reaction time is 0.5 to 2 hours.

9. The method for preparing the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant according to claim 6, 7, or 8, characterized in that, In step (2), the reaction temperature is 80-120℃ and the reaction time is 4-12h.

10. The application of the chlorine-free organic counterionic quaternary ammonium salt gemini surfactant of claim 1 in disinfection, sterilization, oil extraction, and printing and dyeing.

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