Soybean-based morpholine quaternary ammonium salt and preparation method thereof

Abstract

The invention relates to the technical field of organic synthesis, in particular to soybean-based morpholine quaternary ammonium salt and a preparation method thereof, the structural formula of the soybean-based morpholine quaternary ammonium salt is shown as (I), the preparation method comprises the following steps: S1, assembling soybean fatty acid and morpholine or morpholine derivatives through amidation reaction or esterification reaction, and after the reaction is finished, purifying to obtain soybean-based morpholine quaternary ammonium salt; a soybean-based quaternary ammonium salt synthesis precursor is obtained; and S2, placing the soy-based morpholine quaternary ammonium salt synthesis precursor and an alkylating reagent in a solvent for reaction, and after the reaction is finished, purifying to obtain the soy-based morpholine quaternary ammonium salt. The soy-based morpholine quaternary ammonium salt is prepared through a two-step one-pot method, the method is simple in synthesis process and environmentally friendly, and no catalyst or strong acid or strong base needs to be added in the reaction process.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and more specifically, to a soybean-based morpholine quaternary ammonium salt and its preparation method. Background Technology

[0002] Quaternary ammonium salts, as an important class of cationic surfactants, are widely used in bactericides, deodorizers, softeners, corrosion inhibitors, and phase transfer catalysts. With the strengthening of environmental regulations (such as the EU REACH and the US EPA standards), the use of traditional petroleum-based quaternary ammonium salt surfactants (such as long-chain alkyl halides) is becoming increasingly restricted due to their non-renewable nature, high environmental accumulation, and poor biodegradability. Bio-based surfactants are gradually becoming a research hotspot.

[0003] Soybean-based (derived from soybean fatty acids) is an inexpensive, renewable, and biodegradable natural raw material with a long carbon chain hydrophobic structure. It can be modified through reactions such as esterification and amidation to prepare surface-active derivatives, aligning with the trend of green chemistry and making it an ideal alternative to petroleum-based products. Morpholine rings, due to their nitrogen-containing heterocyclic structure, can enhance the water solubility and bioactivity of molecules and are often used to construct functional quaternary ammonium salts. However, existing methods for synthesizing quaternary ammonium salts combining soybean-based and morpholine rings are rarely reported, and they suffer from drawbacks such as complex processes (requiring catalysts / strong acids / bases), insufficient water solubility of the products, and difficulties in purification, which limit their large-scale application.

[0004] Referring to Chinese invention patent application CN115745814A, a method for preparing soybean oil ester-based quaternary ammonium salt is disclosed. The method uses soybean oil, triethanolamine, and dimethyl sulfate as raw materials. Through the esterification reaction of soybean oil and triethanolamine, fatty acid triethanolamine ester is obtained. Then, the fatty acid triethanolamine ester obtained by the esterification reaction is reacted with dimethyl sulfate to obtain soybean oil ester-based quaternary ammonium salt. In the esterification reaction, the reaction temperature is controlled at 60°C and the reaction time is 8 hours. Soybean lipase is added as a catalyst and the reaction is carried out in an inert gas environment.

[0005] Referring to Chinese invention patent document CN110776611B, a soybean oil-based polymeric surfactant and its preparation method are disclosed. This method first involves esterifying epoxidized soybean oil with acrylic acid to obtain acrylate epoxidized soybean oil. Then, the acrylate epoxidized soybean oil containing lipophilic groups is copolymerized with allyl polyoxyethylene ether containing hydrophilic groups via a free radical copolymerization reaction to finally obtain a soybean oil-based polyether surfactant. The esterification reaction requires the addition of triethylamine (catalyst) and a polymerization inhibitor, while the copolymerization reaction requires the addition of an oil-soluble initiator.

[0006] Summarizing the existing methods for synthesizing soybean-based quaternary ammonium salts, it is clear that most of the relatively mature and widely used methods for synthesizing soybean-based quaternary ammonium salt surfactants require the addition of catalysts, inert gas protection, and the addition of various organic solvents for extraction and washing. Therefore, how to synthesize soybean-based quaternary ammonium salts under mild (catalyst-free, acid-free, alkali-free) and green conditions is a problem that needs to be solved by those skilled in the art. Summary of the Invention

[0007] In view of this, the purpose of the present invention is to provide a soybean-based morpholine quaternary ammonium salt and its preparation method, so as to overcome the shortcomings of the prior art.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution: In a first aspect, the present invention provides a soybean-based morpholine quaternary ammonium salt, the structural formula of which is shown in (I):

[0009] Among them, R 1 It is soybeanyl acyl, soybeanyl acyl ethyl, soybeanyl acyl propyl, soybeanyl ester ethyl, or soybeanyl ester propyl; R 2 X is ethyl (-CH2CH3) or methyl (-CH3); X is ethyl sulfate (-CH3CH2OSO3) or iodine (-I).

[0010] Specifically, the structural formulas of soybean acyl, soybean acyl ethyl, soybean acyl propyl, soybean ester ethyl, and soybean ester propyl are shown below in sequence: Furthermore, in the above structural formula, R represents soybean base.

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned soybean-based morpholine quaternary ammonium salt, comprising the following steps: S1. Soybean fatty acids are assembled with morpholine or morpholine derivatives via amidation or esterification reactions. After the reaction is completed, the mixture is purified to obtain the precursor for the synthesis of soybean-based morpholine quaternary ammonium salt. S2. The precursor for the synthesis of soybean-based morpholine quaternary ammonium salt and the alkylating agent were placed in a solvent and reacted. After the reaction was completed, the mixture was purified to obtain soybean-based morpholine quaternary ammonium salt.

[0012] The soybean-based morpholine quaternary ammonium salt prepared by the above method is in the form of a powder solid or an oily liquid.

[0013] In a preferred embodiment, in step S1, the morpholine derivative is 2-morpholine ethanol, 3-morpholine propanol, N -(3-aminopropyl)morpholine and N One or more of (2-aminoethyl)morpholine.

[0014] In the preferred embodiment, in step S1, the molar ratio of soybean fatty acid to morpholine or morpholine derivative is 1:(1~2); more preferably, the molar ratio of soybean fatty acid to morpholine or morpholine derivative is 1:1.1.

[0015] Specifically, 2-morpholinoethanol, 3-morpholinopropanol, N -(3-aminopropyl)morpholine and N The structural formulas of -(2-aminoethyl)morpholine are shown below:

[0016] In a preferred embodiment, in step S1, the reaction conditions for amidation or esterification are: reaction at 120~150℃ for 5~8h, without the need for a reaction solvent; more preferably, the reaction conditions for amidation are: reaction at 150℃ for 5h; even more preferably, the reaction conditions for esterification are: reaction at 150℃ for 5h.

[0017] In a preferred embodiment, in step S1, an azeotropic agent is added to the system of the amidation or esterification reaction. The azeotropic agent is used to separate the water generated during the reaction, thereby promoting the forward reaction.

[0018] In a preferred embodiment, in step S1, the azeotropic agent is one or more of cyclohexane and toluene. More preferably, the azeotropic agent is cyclohexane.

[0019] In a preferred embodiment, in step S2, the alkylating agent is one or more of diethyl carbonate, diethyl sulfate, dimethyl sulfate, iodomethane, and iodoethane.

[0020] In the preferred embodiment, in step S2, the molar ratio of the soybean-based quaternary ammonium salt synthesis precursor to the alkylating agent is 1:(1~2); more preferably, the molar ratio of the soybean-based quaternary ammonium salt synthesis precursor to the alkylating agent is 1:1.1.

[0021] In a preferred embodiment, in step S2, the solvent is one or more of acetonitrile, dichloromethane, ethanol, methanol, tetrahydrofuran, and dimethyl sulfoxide; more preferably, the solvent is acetonitrile.

[0022] In the preferred embodiment, the reaction conditions for step S2 are: reacting at 50~70℃ for 5~7h.

[0023] In the preferred embodiment, in step S2, the purification involves filtering, washing or extracting the crude soybean-based morpholine quaternary ammonium salt product, followed by vacuum distillation to obtain soybean-based morpholine quaternary ammonium salt.

[0024] In a preferred embodiment, in step S2, the extractant used for extraction is water and ethyl acetate.

[0025] The soybean morpholine quaternary ammonium salt prepared by the method provided by this invention is an apricot-yellow oily, brown oily, or yellowish-brown powder. It is completely soluble in water, requires no solubilizer, and its low-concentration aqueous solution is a clear solution with a certain fruity aroma.

[0026] Beneficial effects of the present invention (1) The present invention prepares soybean-based morpholine quaternary ammonium salt by a two-step one-pot method. The synthesis process is simple, green and environmentally friendly, and no catalyst, strong acid / strong base needs to be added during the reaction.

[0027] (2) This invention uses soybean fatty acids and morpholine or its derivatives as raw materials. Soybean fatty acids are a natural and renewable resource, inexpensive, and biodegradable, which aligns with the trend of green chemistry and reduces dependence on petrochemical raw materials. The introduction of the morpholine ring can enhance molecular polarity and improve water solubility and emulsifying properties. Compared with traditional petroleum-based surfactants, this system is more environmentally friendly and suitable for developing bio-based products.

[0028] (3) The soybean-based morpholine quaternary ammonium salt surfactant synthesized in this invention has excellent performance, is completely soluble in water, and has a controllable morphology (the product is a powder solid or an oil liquid, which is convenient for different application scenarios). No solubilizer needs to be added. The low-concentration aqueous solution is a clear solution. Shaking the aqueous solution produces a large number of bubbles. The product itself has a certain fruity aroma. Fragrance can be added or not. The product has a certain deodorizing effect. Furthermore, the purification is efficient and low-cost. The crude product can be purified by conventional operations such as filtration, washing or extraction, and vacuum distillation, which significantly reduces the threshold for industrialization.

[0029] (4) The morpholine derivatives selected in this invention have a variety of monomers with different functions, and a variety of different cationic surfactants can be obtained according to the needs. At the same time, the morpholine derivatives have a high degree of commercialization, can be obtained through a variety of means, are relatively inexpensive, have high product purity, and the process of synthesizing surfactants using morpholine derivatives is economically feasible overall. Attached Figure Description

[0030] Figure 1 This is the gas chromatogram of soybean-based acylmorpholine 1 prepared in Example 1; Figure 2 This is the gas chromatogram of soybean-based acyl ethyl morpholine sulfate 2 prepared in Example 1; Figure 3 This is the 1H NMR spectrum of soybean-based acyl methoxymethyl morpholine 2 prepared in Example 1; Figure 4 This is the gas chromatogram of soybean-based acylethylmorpholine 3 prepared in Example 2; Figure 5 This is the gas chromatogram of soybean-based acylethyl ethyl sulfate ethylmorpholine 4 prepared in Example 2; Figure 6This is the 1H NMR spectrum of soybean-based acylethyl ethyl sulfate ethylmorpholine 4 prepared in Example 2; Figure 7 This is the gas chromatogram of soybean-based ester ethylmorpholine 5 prepared in Example 3; Figure 8 This is the gas chromatogram of soybean-based ethyl morpholine sulfate 6 prepared in Example 3; Figure 9 This is the 1H NMR spectrum of soybean-based ester-based ethyl morpholine sulfate 6 prepared in Example 3; Figure 10 This is the gas chromatogram of soybean-based acylpropylmorpholine 7 prepared in Example 4; Figure 11 This is the gas chromatogram of soybean-based acylpropyl ethylmorpholine 8 prepared in Example 4; Figure 12 This is the 1H NMR spectrum of soybean-based acylpropyl sulfate ethylmorpholine 8 prepared in Example 4; Figure 13 This is the gas chromatogram of soybean-based propylmorpholine 9 prepared in Example 5; Figure 14 This is the gas chromatogram of soybean-based propyl sulfate ethylmorpholine 10 prepared in Example 5; Figure 15 This is the 1H NMR spectrum of soybean-based propyl sulfate ethylmorpholine 10 prepared in Example 5; Figure 16 This is the gas chromatogram of soybean-based acyl iodomethyl morpholine 11 prepared in Example 6; Figure 17 This is the 1H NMR spectrum of soybean-based acyl iodomethyl morpholine 11 prepared in Example 6; Figure 18 This is the gas chromatogram of soybean-based acyl iodoethyl morpholine 12 prepared in Example 7; Figure 19 This is the 1H NMR spectrum of soybean-based acyl iodoethyl morpholine 12 prepared in Example 7; Figure 20 This is a gas chromatogram of the odor source before the deodorizer was sprayed; Figure 21 and 22 This is a gas chromatogram of the odor source after the deodorizing agent has been sprayed. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0032] Unless otherwise stated, scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. Unless otherwise specified, the experimental methods used in the examples are conventional methods. Where specific conditions are not specified in the examples, they should be performed under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0033] In the following examples, the serial numbers such as 1, 2, ... appearing in the names of the synthesized products are only for the purpose of distinguishing the synthesized products and have no special meaning, nor are they used to limit the synthesized products.

[0034] Example 1

[0035] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based acylmorpholine 1: 250 mmol of soybean fatty acid and 750 mmol of morpholine were added to a 500 mL three-necked flask, along with 40 mL of cyclohexane. A water separator and thermometer were installed, and the mixture was refluxed at 150 °C for 5 hours. The system was kept sealed throughout the reaction. After the reaction, the resulting dark red solution was subjected to vacuum distillation (gauge pressure -0.095 MPa, temperature 75 °C) to remove unreacted morpholine and the dehydrating agent cyclohexane, yielding a pure solution, which is soybean-based acylmorpholine 1. The structural formula of soybean-based acylmorpholine 1 is as follows:

[0036] S2. Synthesis of soybean-based acyl sulfate ethylmorpholine 2: Add 40 mL of acetonitrile to a 250 mL round-bottom flask, followed by 155 mmol of soybean-based ethyl morpholine 1 and 155 mmol of diethyl sulfate. After mixing, react at 70 °C for 6 h. After the reaction is complete, extract the solution with water and ethyl acetate (total 100 mL, water to ethyl acetate ratio 3:1). After the solution separates into layers, collect the lower water layer in a flask and remove the acetonitrile and water by vacuum distillation (gauge pressure -0.095 MPa, temperature 68 °C), yielding a dark brown oily substance, which is soybean-based ethyl morpholine sulfate 2. The structural formula of soybean-based ethyl morpholine sulfate 2 is as follows:

[0037] The soybean-based acylmorpholine 1 and soybean-based acylsulfate ethylmorpholine 2 synthesized in this embodiment were subjected to meteorological characterization, and the characterization results are shown in Tables 1-2. Figures 1-2 As shown.

[0038] Table 1. Gas-phase characteristics of soybean-based acylmorpholine 1

[0039] The yield of soybean-based acylmorpholine 1 was calculated to be 88% based on the gas phase characteristics of soybean-based acylmorpholine 1. Figure 1 This is the gas chromatogram of soybean-based acylmorpholine 1.

[0040] Table 2. Gas phase characteristics of soybean-based acyl ethyl morpholine sulfate 2.

[0041] Based on the gas-phase characteristics of soybean-based ethyl morpholine sulfate 2, the yield of soybean-based ethyl morpholine sulfate 2 was calculated to be 46.6%. Figure 2 This is the gas chromatogram of soybean acyl sulfate ethylmorpholine 2.

[0042] Figure 3 The 1H NMR spectrum is that of ethylmorpholine 2-soy-acyl sulfate. Figure 3 It can be seen that 0.89-0.86 ppm represents the methyl proton peak at the end of the aliphatic chain; the chemical shift values ​​of 2.25-1.24 ppm represent the methylene proton peak in the aliphatic chain; the chemical shift values ​​of the methylene protons bonded to the anion are 3.75-3.70 ppm; and 4.10-3.40 ppm represent the chemical shifts generated by protons on the morpholine ring. The chemical shifts at 10.1-9.7 ppm are generated by protons bonded to C=O.

[0043] Example 2

[0044] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based acylethylmorpholine 3: 500 mmol of soybean fatty acids and 500 mmol N -(2-Aminoethyl)morpholine was added to a 500 mL three-necked flask, followed by 50 mL of cyclohexane. A water separator and thermometer were installed, and the reaction was carried out at 150 °C for 5 h. Water was separated from the water separator periodically, and the system was kept sealed throughout the reaction. After the reaction was complete, the cyclohexane was removed by vacuum distillation (gauge pressure -0.095 MPa, temperature 40 °C) to obtain soybean-based acylethylmorpholine 3, an amber liquid. The structural formula of soybean-based acylethylmorpholine 3 is as follows:

[0045] S2. Synthesis of soybean-based acylethyl ethyl sulfate ethylmorpholine 4: Add 70 mL of acetonitrile to a 500 mL three-necked flask, followed by 500 mmol of soybean-based ethyl morpholine 3 and 500 mmol of diethyl sulfate. Install a thermometer and reflux at 70 °C for 6 h, maintaining a sealed system throughout the reaction. After the reaction, extract the solution with water and ethyl acetate (total 200 mL, water to ethyl acetate ratio 3:1). After the solution separates into layers, collect the lower water layer in a flask and remove the acetonitrile and water by vacuum distillation (gauge pressure -0.095 MPa, temperature 68 °C), yielding a brown oily substance, which is soybean-based ethyl morpholine sulfate 4. The structural formula of soybean-based ethyl morpholine sulfate 4 is as follows:

[0046] The soybean-based acylethyl morpholine 3 and soybean-based acylethyl sulfate ethyl morpholine synthesized in this embodiment were subjected to meteorological characterization, and the characterization results are shown in Tables 3-4. Figures 4-5 As shown.

[0047] Table 3. Gas phase characteristics of soybean-based acylethylmorpholine 3

[0048] The yield of soybean-based acylethylmorpholine 3 was calculated to be 96.7% based on the gas phase characterization results. Figure 4 This is the gas chromatogram of soybean-based acylethylmorpholine 3.

[0049] Table 4. Gas-phase characteristics of soybean-based acylethyl ethyl sulfate ethylmorpholine 4

[0050] Based on the gas phase characterization results of soybean-based acylethyl ethyl sulfate ethylmorpholine 4, the yield of soybean-based acylethyl ethyl sulfate ethylmorpholine 4 was calculated to be 68.8%. Figure 5 This is the gas chromatogram of soybean acyl ethyl sulfate ethylmorpholine 4.

[0051] Figure 6 The 1H NMR spectrum of soybean acylethyl ethyl sulfate ethylmorpholine 4 is shown. Figure 6 It can be seen that 0.92-0.80 ppm represents the methyl proton peak at the end of the aliphatic chain; the chemical shift value of 2.25-1.18 ppm represents the methylene proton peak in the aliphatic chain; the chemical shift value of the methylene proton connected to the anion is 3.73-3.68 ppm; 4.10-3.40 ppm represents the chemical shift produced by the proton on the morpholine ring; and 8.02-7.91 ppm represents the chemical shift produced by the proton at O=CN.

[0052] Example 3

[0053] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based ethylmorpholine 5: 600 mmol of soybean fatty acid and 600 mmol of 2-morpholine ethanol were added to a 500 mL three-necked flask, along with 50 mL of cyclohexane. A water separator and thermometer were installed, and the mixture was reacted at 150 °C for 5 h. Water was separated from the water separator periodically, and the system was kept sealed throughout the reaction. After the reaction was complete, the cyclohexane was removed by vacuum distillation (gauge pressure -0.095 MPa, temperature 40 °C) to obtain soybean-based ethylmorpholine 5, an amber liquid. The structural formula of soybean-based ethylmorpholine 5 is as follows:

[0054] S2. Synthesis of soybean-based ethyl morpholine sulfate 6: Add 70 mL of acetonitrile to a 500 mL three-necked flask, followed by 600 mmol of soy-based ethyl morpholine 5 and 600 mmol of diethyl sulfate. Install a thermometer and condenser, and reflux at 70 °C for 6 h, maintaining a sealed system throughout the reaction. After the reaction, extract the solution with water and ethyl acetate (total 200 mL, water to ethyl acetate ratio 3:1). After the solution separates into layers, collect the lower water layer in a flask and remove the acetonitrile and water by vacuum distillation (gauge pressure -0.095 MPa, temperature 68 °C), yielding an apricot-yellow oily substance, which is soy-based ethyl morpholine sulfate 6. The structure of soy-based ethyl morpholine sulfate 6 is as follows:

[0055] The soybean-based ester-based ethyl morpholine 5 and soybean-based ester-based ethyl sulfate ethyl morpholine 6 synthesized in this embodiment were subjected to meteorological characterization, and the characterization results are shown in Tables 5-6. Figures 7-8 As shown.

[0056] Table 5. Gas phase characteristics of soybean-based ethylmorpholine 5

[0057] Based on the gas phase characteristics of soybean-based ethyl morpholine 5, the yield of soybean-based ethyl morpholine 5 was calculated to be 91.4%. Figure 7 This is the gas chromatogram of soybean-based ethylmorpholine 5.

[0058] Table 6. Gas phase characterization results of soybean-based ethyl morpholine sulfate 6.

[0059] Based on the gas phase characterization results of soybean-based ethyl morpholine sulfate 6, the yield of soybean-based ethyl morpholine sulfate 6 was calculated to be 89%. Figure 8 This is a gas chromatogram of soybean-based ethyl morpholine sulfate 6.

[0060] Figure 9 The 1H NMR spectrum of soybean-based ethyl morpholine sulfate 6 is shown. Figure 9 It can be seen that 0.89-0.86 ppm represents the methyl proton peak at the end of the aliphatic chain; the chemical shift values ​​of 2.40-1.21 ppm represent the methylene proton peak in the aliphatic chain; the chemical shift values ​​of the methylene protons bonded to the anion are 3.77-3.67 ppm; and 4.15-3.34 ppm represent the chemical shifts generated by protons on the morpholine ring. The protons of the unsaturated double bonds in the side chain correspond to chemical shifts of 5.40-4.52 ppm; the chemical shifts of 9.68-9.57 ppm are generated by protons bonded to C=O.

[0061] Example 4

[0062] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based acylpropylmorpholine 7: 500 mmol of soybean fatty acids and 500 mmol N -(3-aminopropyl)morpholine was added to a 500 mL three-necked flask, followed by 50 mL of cyclohexane. A water separator and thermometer were installed, and the reaction was carried out at 150 °C for 5 h. Water was separated from the water separator periodically. After the reaction was complete, the cyclohexane was removed by vacuum distillation (gauge pressure -0.095 MPa, temperature 40 °C) to obtain soybean-based acylpropylmorpholine 7, an amber liquid. The structural formula of soybean-based acylpropylmorpholine 7 is as follows:

[0063] S2. Synthesis of soybean-based acylpropyl sulfate ethylmorpholine 8: Add 70 mL of acetonitrile to a 500 mL three-necked flask, followed by 400 mmol of soybean-based acylpropylmorpholine 7 and 400 mmol of diethyl sulfate. Install a thermometer and condenser, and reflux at 70 °C for 6 h, maintaining a sealed system throughout the reaction. After the reaction, extract the solution with water and ethyl acetate (total 200 mL, water to ethyl acetate ratio 3:1). After the solution separates into layers, collect the lower water layer in a flask and remove the acetonitrile and water by vacuum distillation (gauge pressure -0.095 MPa, temperature 68 °C). The resulting yellow oily substance is soybean-based acylpropylmorpholine 8. The structural formula of soybean-based acylpropylmorpholine 8 is as follows:

[0064] The soybean-based acylpropylmorpholine 7 and soybean-based acylpropyl sulfate ethylmorpholine 8 synthesized in this embodiment were characterized by gas chromatography, and the characterization results are shown in Tables 7-8. Figures 10-11 As shown in the figure.

[0065] Table 7. Gas-phase characteristics of soybean-based acylpropylmorpholine 7

[0066] Based on the gas phase characteristics of soybean-based acylpropylmorpholine 7, the yield of soybean-based acylpropylmorpholine 7 was calculated to be 98.5%. Figure 10 This is the gas chromatogram of soybean-based acylpropylmorpholine 7.

[0067] Table 8. Gas phase characteristics of soybean-based acylpropyl ethylmorpholine 8.

[0068] Based on the gas phase characteristics of soybean acylpropyl ethyl morpholine sulfate 8, the yield of soybean acylpropyl ethyl morpholine sulfate 8 was calculated to be 54.7%. Figure 11 This is the gas chromatogram of soybean acylpropyl sulfate ethylmorpholine 8.

[0069] Figure 12 The 1H NMR spectrum of soybean acylpropyl sulfate ethylmorpholine 8 is shown. Figure 12 It can be seen that 0.92-0.81 ppm represents the methyl proton peak at the end of the aliphatic chain; the chemical shift values ​​of 2.28-1.21 ppm represent the methylene proton peak in the aliphatic chain; the chemical shift values ​​of the methylene protons connected to the anion are 3.70-3.65 ppm; and 4.14-3.42 ppm represent the chemical shifts generated by protons on the morpholine ring. The protons of the unsaturated double bonds in the side chain correspond to chemical shifts of 5.45-4.56 ppm; and 8.11-7.91 ppm represent the chemical shifts generated by protons at the O=CN junction.

[0070] Example 5

[0071] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based propylmorpholine 9: 500 mmol of soybean fatty acid and 500 mmol of 3-morpholinopropanol were added to a 500 mL three-necked flask, along with 50 mL of cyclohexane. A water separator and thermometer were installed, and the mixture was reacted at 150 °C for 5 h. Water was separated from the water separator periodically. After the reaction was complete, the cyclohexane was removed by vacuum distillation (gauge pressure -0.095 MPa, temperature 40 °C) to obtain soybean-based propylmorpholine, an amber liquid. The structural formula of soybean-based propylmorpholine 9 is as follows:

[0072] S2. Synthesis of soybean-based propyl ester ethylmorpholine 10: Add 70 mL of acetonitrile to a 500 mL three-necked flask, followed by 400 mmol of soybean fatty acid morpholine propyl ester 9 and 400 mmol of diethyl sulfate. Install a thermometer and condenser, and reflux at 70 °C for 6 h, maintaining a sealed system throughout the reaction. After the reaction, extract the solution with water and ethyl acetate (total 200 mL, water to ethyl acetate ratio 3:1). After the solution separates into layers, collect the lower water layer in a flask and remove the acetonitrile and water by vacuum distillation (gauge pressure -0.095 MPa, temperature 68 °C). The resulting apricot-yellow oily substance is soybean-based propyl methylmorpholine sulfate 10. The structural formula of soybean-based propyl methylmorpholine sulfate 10 is as follows:

[0073] The soybean-based propylmorpholine 9 and soybean-based propyl sulfate ethylmorpholine 10 synthesized in this embodiment were characterized by gas chromatography, and the characterization results are shown in Tables 9-10. Figures 13-14 As shown.

[0074] Table 9. Gas-phase characteristics of soybean-based propylmorpholine 9

[0075] Based on the gas phase characteristics of soybean-based propylmorpholine 9, the yield of soybean-based propylmorpholine 9 was calculated to be 97.6%. Figure 13 This is the gas chromatogram of soybean-based propylmorpholine 9.

[0076] Table 10 Gas-phase characteristics of soybean-based propyl methyl methacrylate 10

[0077] Based on the gas phase characteristics of soybean-based propyl methyl morpholine sulfate 10, the yield of soybean-based propyl methyl morpholine sulfate 10 was calculated to be 77%. Figure 14 This is the gas chromatogram of soybean-based propyl sulfate ethylmorpholine 10.

[0078] Figure 15 The 1H NMR spectrum of soybean-based propyl sulfate ethylmorpholine 10 is shown. Figure 15It can be seen that chemical shift values ​​of 2.17–1.10 ppm represent the methylene proton peak in the aliphatic chain; the chemical shift values ​​of the methylene protons bonded to the anion are 3.70–3.55 ppm; and 4.12–2.96 ppm represent the chemical shifts generated by protons on the morpholine ring. The protons of the unsaturated double bonds in the side chain correspond to chemical shifts at 5.40–4.52 ppm. The chemical shifts at 9.71–9.20 ppm are generated by protons bonded to C=O.

[0079] Example 6

[0080] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based acylmorpholine 1: The steps are the same as step S1 in Example 1.

[0081] S2. Synthesis of soybean-based acyl iodomethyl morpholine 11: Add 200 mmol of soybean-based methylmorpholine 1 to a 250 mL round-bottom flask, followed by 200 mmol of iodomethane. React at 70 °C for 6 h, maintaining a sealed system throughout the reaction. After the reaction is complete, filter the solid and repeatedly wash it with petroleum ether to remove residual soybean-based methylmorpholine 1 and iodomethane. After several washes, transfer the solid to a flask and distill under reduced pressure (gauge pressure -0.095 MPa, temperature 35 °C) to remove the petroleum ether from the surface, yielding a dry, yellowish-brown solid, which is the synthesized soybean-based methylmorpholine 11. The structural formula of soybean-based methylmorpholine 11 is as follows:

[0082] The soybean-based acyl iodide methyl morpholine 11 prepared in this embodiment was characterized by gas chromatography. The characterization results are shown in Table 11 and... Figure 16 As shown.

[0083] Table 11 Gas-phase characteristics of soybean-based acyl iodomethyl morpholine 11

[0084] Based on the gas-phase characteristics of soybean-based acyl iodomethyl morpholine 11, the yield of soybean-based acyl iodomethyl morpholine 11 was calculated to be 86.2%. Figure 16 The gas chromatogram of soybean-based acyliodomethylmorpholine 11.

[0085] Figure 17 The 1H NMR spectrum of soybean-based acyliodomethylmorpholine 11. Figure 17It can be seen that 0.93-0.80 ppm represents the methyl proton peak at the end of the aliphatic chain; the chemical shift values ​​of 2.37-1.18 ppm represent the methylene proton peak in the aliphatic chain; and 4.29-3.21 ppm represent the chemical shifts caused by protons on the morpholine ring. The protons of the unsaturated double bonds in the side chain correspond to chemical shifts at 5.40-5.18 ppm; 9.36-9.16 ppm represent the chemical shifts caused by protons bonded to O=C.

[0086] Example 7

[0087] A method for preparing a soybean-based morpholine quaternary ammonium salt includes the following steps: S1. Synthesis of soybean-based acylmorpholine 1: The steps are the same as step S1 in Example 1.

[0088] S2. Synthesis of soybean-based acyl iodoethyl morpholine 12: Add 200 mmol of soybean-based acylmorpholine 1 to a 250 mL round-bottom flask, followed by 200 mmol of iodoethane. React at 70 °C for 6 h, keeping the system sealed throughout the reaction. After the reaction, filter the solid and repeatedly wash it with petroleum ether to remove residual soybean-based acylmorpholine 1 and iodoethane. After several washes, transfer the solid to a flask and distill under reduced pressure (gauge pressure -0.095 MPa, temperature 35 °C) to remove the petroleum ether from the surface, yielding a yellowish-brown solid, which is soybean-based acyl iodoethylmorpholine 12. The structural formula of soybean-based acyl iodoethylmorpholine 12 is as follows:

[0089] The gas phase characterization of soybean-based acyl iodoethyl morpholine 12 prepared in this embodiment was performed, and the characterization results are shown in Table 12 and... Figure 18 As shown.

[0090] Table 12 Gas phase characteristics of soybean-based acyl iodoethyl morpholine 12

[0091] Based on the gas phase characteristics of soybean-based acyl iodoethyl morpholine 12, the yield of soybean-based acyl iodoethyl morpholine 12 was calculated to be 91.9%. Figure 18 This is the gas chromatogram of soybean-based acyl iodoethyl morpholine 12.

[0092] Figure 19 The 1H NMR spectrum of soybean-based acyliodoethylmorpholine 12. Figure 19It can be seen that 0.91-0.81 ppm represents the methyl proton peak at the end of the aliphatic chain; the chemical shift values ​​of 2.34-1.18 ppm represent the methylene proton peak in the aliphatic chain; and 4.10-3.02 ppm represent the chemical shifts caused by protons on the morpholine ring. The protons of unsaturated double bonds in the side chain correspond to chemical shifts of 5.40-5.18 ppm; the protons of unsaturated double bonds in the side chain correspond to chemical shifts of 5.25-4.97 ppm; and 8.77-8.31 ppm represent the chemical shifts caused by protons bonded to O=C.

[0093] Comparative Example 1 Cetyl ethylmorpholine nitrogen ethyl sulfate, purchased from Shaanxi Didu Pharmaceutical Chemical Co., Ltd., purity: 0.99, EINECS: 201-094-8, CAS: 78-21-7.

[0094] Odor removal was compared using cetyl ethyl morpholine nitrogen ethyl sulfate provided in Comparative Example 1 and soybean-based morpholine quaternary ammonium salt prepared in Example 3.

[0095] Comparative properties: Odor neutralizer, white to pale yellow solid or paste in appearance, soluble in polar solvents such as water and ethanol, melting point is about 50~70℃ (depending on purity), pH value (1% aqueous solution) is about 4~7, surface activity is cationic, and it has excellent antistatic and softening properties.

[0096] The deodorization process of soybean-based morpholine quaternary ammonium salt prepared in Example 3 and cetyl ethyl morpholine azinon ethyl sulfate in Comparative Example 1 is compared as follows: Odor sources: 5% ethyl mercaptoside solution, 5% triethylamine solution, 5% benzyl mercaptoside solution, and 5% o-phenylenediamine solution.

[0097] Deodorizers: 2% soybean ester ethyl sulfate ethylmorpholine 6 solution, 2% cetyl ethylmorpholine nitrogen ethyl sulfate solution.

[0098] Odor removal process: Take a certain number of beakers and spray the odor source into each beaker 5 times (dosage: 0.15mL / 50cm² each time). 3 (Time interval: 1 second), followed by spraying soybean-based ethyl morpholine sulfate 6 solution and cetyl ethyl morpholine nitrogen ethyl sulfate solution 8 times each (dosage: 0.15 mL / 50 cm² each time). 3 (Time interval: 1 second). After spraying, place the beaker in a sealed environment for 1 hour. After the time is up, take a certain amount of sample and start gas phase detection.

[0099] Gas chromatography characterization: Peak areas of odor sources before spraying the deodorizing agent (Table 13) and peak areas of odor sources after spraying the deodorizing agent (Table 14). The gas chromatogram of the odor source before spraying the deodorizing agent is shown below. Figure 20 As shown.

[0100] Table 13 Peak area of ​​odor sources before odor removal agent was sprayed

[0101] Table 14 Peak area of ​​odor sources after spraying deodorizing agent

[0102] Figure 21 Gas chromatograms showing the changes in odor source peak area after spraying the deodorizing agent of Example 3 and Comparative Example 1; where the characteristic peak of triethylamine is at 4.5 min. Figure 21 In the text, the green peak corresponds to the deodorizer in Example 1, and the orange-yellow peak corresponds to the deodorizer in Example 3. The characteristic peak of ethyl mercaptoacetate is located at 7.3 min. Figure 21 In the diagram, the blue peak corresponds to the deodorizer in Example 1, and the purple peak corresponds to the deodorizer in Example 3.

[0103] Figure 22 The gas chromatograms show the changes in the peak area of ​​the odor source after spraying the deodorizing agent of Example 3 and Comparative Example 1; among them, the characteristic peak of benzyl mercaptan is at 9.3 min. Figure 22 In the text, the purple peak corresponds to the deodorizer in Example 1, and the green peak corresponds to the deodorizer in Example 3. The characteristic peak of o-phenylenediamine is located at 11.9 min. Figure 22 In the diagram, the orange-yellow peak corresponds to the deodorizer in Example 1, and the red peak corresponds to the deodorizer in Example 3.

[0104] Deodorization rate =

[0105] Table 15 Odor removal rate of odor removers on odor sources

[0106] As can be seen from the data in Tables 13-15 and the gas chromatograms above, both have deodorizing effects on the aforementioned odor sources. In the deodorizing effect test, different deodorizing agents exhibited different deodorizing rates for ethyl mercaptoethyl, triethylamine, benzyl mercaptan, and o-phenylenediamine. The deodorizing agent containing cetyl ethylmorpholine azinon ethyl sulfate showed deodorizing rates of 75.3%, 71.5%, 69.4%, and 74.9% for the above four substances, respectively; while the deodorizing agent containing soy-based ester-based ethylmorpholine sulfate showed better results, with deodorizing rates reaching 83.1%, 85.7%, 80.7%, and 83.1%, respectively. Overall, soy-based ester-based ethylmorpholine sulfate 6 exhibits superior deodorizing performance compared to cetyl ethylmorpholine azinon ethyl sulfate.

[0107] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A soybean-based morpholine quaternary ammonium salt, characterized in that, Its structural formula is shown in (Ⅰ): Among them, R 1 It is soybeanyl acyl, soybeanyl acyl ethyl, soybeanyl acyl propyl, soybeanyl ester ethyl, or soybeanyl ester propyl; R 2 X is ethyl or methyl; X is ethyl sulfate or iodine.

2. A method for preparing soybean-based morpholine quaternary ammonium salt according to claim 1, characterized in that, Includes the following steps: S1. Soybean fatty acids are assembled with morpholine or morpholine derivatives via amidation or esterification. After the reaction is completed, the mixture is purified to obtain the soybean-based quaternary ammonium salt synthesis precursor. S2. The precursor for the synthesis of soybean-based morpholine quaternary ammonium salt and the alkylating agent were placed in a solvent and reacted. After the reaction was completed, the mixture was purified to obtain soybean-based morpholine quaternary ammonium salt.

3. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, In step S1, the morpholine derivative is 2-morpholine ethanol, 3-morpholine propanol, N -(3-aminopropyl)morpholine and N One or more of (2-aminoethyl)morpholine; the molar ratio of soybean fatty acid to morpholine or morpholine derivative is 1:(1~3).

4. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, In step S1, the conditions for the amidation or esterification reaction are: reaction at 120~150℃ for 5~8h.

5. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, In step S1, an azeotropic agent is added to the system of the amidation reaction or esterification reaction; the azeotropic agent is one or more of cyclohexane and toluene.

6. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, In step S2, the alkylating agent is one or more of diethyl carbonate, diethyl sulfate, dimethyl sulfate, iodomethane, and iodoethane; the molar ratio of the soybean-based morpholine quaternary ammonium salt synthesis precursor to the alkylating agent is 1:(1~2).

7. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, In step S2, the solvent is one or more of acetonitrile, dichloromethane, and ethanol.

8. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, The reaction conditions for step S2 are: react at 50~70℃ for 5~7h.

9. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 2, characterized in that, In step S2, the purification involves filtering, washing or extracting the crude soybean-based morpholine quaternary ammonium salt product, followed by vacuum distillation to obtain soybean-based morpholine quaternary ammonium salt.

10. The method for preparing soybean-based morpholine quaternary ammonium salt according to claim 9, characterized in that, In step S2, the extractant used for extraction is water and ethyl acetate.

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