CN113600097A - Preparation method of asymmetric gemini imidazoline phosphate surfactant - Google Patents

Preparation method of asymmetric gemini imidazoline phosphate surfactant Download PDF

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CN113600097A
CN113600097A CN202110824766.1A CN202110824766A CN113600097A CN 113600097 A CN113600097 A CN 113600097A CN 202110824766 A CN202110824766 A CN 202110824766A CN 113600097 A CN113600097 A CN 113600097A
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acid
phosphate
imidazoline
gemini imidazoline
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CN113600097B (en
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张高飞
张威
王丰收
刘兵
司丽丽
李蕊
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SHANGHAI FINE CHEMICAL CO Ltd
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Abstract

The invention discloses a preparation method of an asymmetric gemini imidazoline phosphate surfactant, which comprises the following steps: step one, synthesizing an asymmetric gemini imidazoline intermediate: secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution: step three, alkylation reaction: according to the invention, organic alkali is used for replacing inorganic alkali, 3-chloro-2-hydroxyl propyl ammonium phosphate is not easy to hydrolyze during alkylation, the asymmetrical gemini imidazoline phosphate salt surfactant obtained by directly reacting 3-chloro-2-hydroxyl propyl ammonium phosphate aqueous solution has good water solubility, more excellent corrosion inhibition performance on metal, safe and environment-friendly raw materials, simple reaction process, high yield and atom utilization rate, suitability for industrial large-scale production, accordance with the green development direction of the current corrosion prevention technology, and forcefully promotes the development and innovation of the corrosion prevention technology in China.

Description

Preparation method of asymmetric gemini imidazoline phosphate surfactant
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a preparation method of an asymmetric gemini imidazoline phosphate surfactant.
Background
Metal corrosion is one of the main causes of equipment life shortening, resulting in production down-time and environmental pollution. Practice proves that the corrosion inhibitor is used in various metal corrosion protection methods, is a method with simple and convenient process, low cost and strong applicability, and is widely applied to the industries of petroleum and natural gas exploitation and refining, machinery, chemical industry, energy and the like. The imidazoline ring is a five-membered ring, wherein two nitrogen atoms and phosphorus atoms can provide lone electron pairs to form coordination bonds with empty orbits of iron atoms, so that the adsorption capacity between corrosion inhibitor molecules and metal is enhanced, imidazoline surfactant molecules are stably adsorbed on the surface of the metal, and the imidazoline surfactant has excellent corrosion inhibition performance on carbon steel, brass, aluminum alloy and the like. Imidazoline corrosion inhibitors have been used in large scale and large scale, but have the problems of poor water solubility, short protection period and the like.
The imidazoline gemini surfactant is divided into a symmetrical type and an asymmetrical type, and the symmetrical imidazoline gemini surfactant is relatively simple in synthesis process, easy to prepare and more in research. Compared with the symmetrical double quaternary ammonium salt, the asymmetric double quaternary ammonium salt has better performance due to the special structure and particularly shows good corrosion inhibition performance in the field of metal corrosion. However, the synthesis process is complex and still in the starting stage, and the synthesis method reported in the prior art has the defects of high raw material toxicity, serious material waste, poor environmental protection, serious lack of economy and incapability of large-scale industrialization.
Patent application publication No. CN112047886A discloses synthesis of oleic acid imidazoline using oleic acid and an amine. Patent application with publication number CN111995578A uses oleic acid to react with diethylenetriamine to synthesize a monocyclic imidazoline intermediate, and then the monocyclic imidazoline intermediate is mixed with dichloroethane to carry out linking reaction to obtain a gemini imidazoline intermediate. Such imidazoline corrosion inhibitors generally have poor water solubility and limited application range.
Disclosure of Invention
Aiming at the technical problems that the imidazoline surfactant in the prior art has poor water solubility and short metal corrosion inhibition protection period, the recrystallization purification period of 3-chloro-2-hydroxyl ammonium propionate phosphate ester is very long, a large amount of organic solvent is needed, and the like, the invention aims to provide a preparation method of the asymmetric gemini imidazoline phosphate ester surfactant, which has simple process, does not use organic solvent, and does not contain organic base.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of an asymmetric gemini imidazoline phosphate surfactant, which comprises the following steps:
step one, synthesizing an asymmetric gemini imidazoline intermediate:
under the protection of nitrogen, adding C8～C18Mixing fatty acid, organic polyamine and phosphoric acid, heating to 100-200 ℃ (preferably 140 ℃) under the condition that the vacuum negative pressure is 1500-30000 Pa (preferably 13000-20000 Pa), reacting for 2-10 h (preferably 2-3 h), and adding C12～C18Heating the fatty acid to 130-250 ℃ in a gradient manner (preferably 160-180 ℃, more preferably 170 ℃), reacting for 1-8 h (preferably 3-4 h), heating to 220-250 ℃ for cyclization reaction until no water is evaporated out, and obtaining an asymmetric gemini imidazoline intermediate;
the phosphoric acid accounts for C8～C18Fatty acids, organic polyamines, C12～C18The mass percentage of the total mass of the fatty acid and the phosphoric acid is 0.01-1%;
said C is8～C18Fatty acid, C12～C18The molar ratio of the fatty acid to the organic polyamine is (0.9-1.1): (0.9-1.1): (0.3 to 1.5);
the organic polyamine is at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
said C is8～C18The fatty acid is one of oleic acid, linoleic acid, myristic acid and lauric acid;
said C is12～C18The fatty acid is one of lauric acid, n-capric acid and n-caprylic acid;
said C is8～C18Fatty acids with said C12～C18The fatty acid is not the same fatty acid at the same time;
secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
dissolving ammonium dihydrogen phosphate in water, wherein the mass ratio of the ammonium dihydrogen phosphate to the water is 1 (5-20) (preferably 1 (5-12)), stirring and heating to 60-100 ℃ (preferably 75-85 ℃), and dropwise adding epoxy chloropropane to react for 1-6 h (preferably 3-5 h) under the condition of condensation reflux to obtain a transparent 3-chloro-2-hydroxypropyl ammonium phosphate aqueous solution;
the molar ratio of the ammonium dihydrogen phosphate to the epoxy chloropropane is (1-2) to 1;
step three, alkylation reaction:
adding the asymmetric gemini imidazoline intermediate and organic base obtained in the first step into the transparent 3-chloro-2-hydroxypropionate ammonium aqueous solution in the second step, stirring and heating to 50-95 ℃, and reacting for 1-10 h (preferably 3-5 h) to obtain an asymmetric gemini imidazoline phosphate surfactant;
the molar ratio of the asymmetric gemini imidazoline intermediate, the 3-chlorine-2 hydroxyl propyl ammonium phosphate and the organic alkali is 1 (1.1-3) to 0.5-3;
the organic alkali is ammonia water, monoethanolamine, diethanolamine or triethanolamine.
The structural formula of the main components of the asymmetric gemini imidazoline phosphate surfactant is as follows:
Figure BDA0003173200120000031
wherein R is1Is C12～C18Fatty acid alkyl radical, R2Is C12～C18A fatty acid alkyl group;
said C is12～C18The fatty acid alkyl group is one of the following groups:
oleic acid alkyl group: CH (CH)3(CH2)7CH＝CH(CH2)7 -
Linoleate alkyl group: CH (CH)3(CH2)4CH＝CHCH2CH＝CH(CH2)7 -
Abietic acid alkyl group:
Figure BDA0003173200120000032
saturated fatty acid group: CH (CH)3(CH2)14-CH3(CH2)16-。
In the first step, the acid value of the asymmetric gemini imidazoline intermediate is 0.2-3 mg KOH/g, and preferably 0.5-2.6 mg KOH/g.
In the first step, the temperature is increased in a gradient manner at a temperature increase rate of 5-25 ℃/h.
In the first step, phosphoric acid is C8～C18Fatty acids, organic polyamines, C12～C18The mass percentage of the total mass of the fatty acid and the phosphoric acid was 0.2%.
In the first step, C8～C18Fatty acid, C12～C18The molar ratio of the fatty acid to the organic polyamine is 1:1 (1.01-1.1).
In the first step, the organic polyamine is diethylenetriamine.
In the second step, the mol ratio of the ammonium dihydrogen phosphate to the epoxy chloropropane is (1.1-1.2): 1.
In the third step, the molar ratio of the asymmetric gemini imidazoline intermediate, the 3-chlorine-2 hydroxyl propyl ammonium phosphate and the organic alkali is 1 (1.1-3) to 1.1-2.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
according to the invention, organic alkali is used for replacing inorganic alkali, 3-chloro-2-hydroxyl propyl ammonium phosphate is not easy to hydrolyze during alkylation, the asymmetrical gemini imidazoline phosphate salt surfactant obtained by directly reacting 3-chloro-2-hydroxyl propyl ammonium phosphate aqueous solution has good water solubility, more excellent corrosion inhibition performance on metals, safe and environment-friendly raw materials, simple reaction process, high yield and atom utilization rate, suitability for industrial large-scale production, accordance with the green development direction of the current anticorrosion technology, and forcefully promotes the development and innovation of the anticorrosion technology in China.
Drawings
FIG. 1 is an infrared spectrum of an asymmetric gemini imidazoline phosphate surfactant prepared according to example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The fatty acid, diethylenetriamine and ammonium dihydrogen phosphate used in the embodiment of the invention are all AR and purchased from Shanghai Tantan science and technology GmbH; ammonium dihydrogen phosphate and epichlorohydrin are both AR and purchased from chemical reagents of national drug group, Inc.; carbon steel sheet, A3Yangzhou Keli environmental protection facilities, Inc.
Example 1
Taking diethylenetriamine as an example, the synthetic route of the invention is as follows:
Figure BDA0003173200120000041
wherein R is1Is C12～C18Fatty acid alkyl radical, R2Is C12～C18Fatty acid alkyl groups.
Oleic acid alkyl group: CH (CH)3(CH2)7CH＝CH(ch2)7 -
Linoleate alkyl group: CH (CH)3(CH2)4CH＝CHCH2CH＝CH(CH2)7 -
Alkyl group of abietic acid：
Figure BDA0003173200120000042
Saturated fatty acid group: CH (CH)3(CH2)14-CH3(CH2)16-。
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding oleic acid (1 mol and 282.5 g) and phosphoric acid (1.2 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 13000pa, heating to 140 ℃, reacting for 3h, adding lauric acid (1 mol and 200.3 g), heating to 170 ℃ at a gradient of 20 ℃/h, reacting for 4h, heating to 250 ℃ for cyclization reaction until no water is evaporated after 4h, cooling to 80 ℃ to obtain an oleic lauric acid imidazoline intermediate 532.7 g, and measuring the acid value to be 2.6mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle equipped with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.36 mol, 41.4 g) was dissolved in 269.1 g of water, the temperature was raised to 85 ℃ under stirring, epichlorohydrin (0.3 mol, 27.8 g) was added under reflux condensation to react for 3 hours, and the epichlorohydrin conversion rate in the solution was determined to be 99.7%, to obtain a transparent 3-chloro-2 hydroxypropanoate ammonium aqueous solution.
Step three, alkylation reaction:
adding the oleic lauric acid imidazoline intermediate (0.15 mol and 79.8 g) prepared in the first step and ammonia water (0.3 mol and 37.5 g) with the mass concentration of 28% into the transparent 3-chloro-2-hydroxypropionic acid ammonium phosphate (0.3 mol) aqueous solution prepared in the second step, stirring and heating to 85 ℃, and reacting for 4 hours to obtain the asymmetric oleic acid lauric acid based gemini imidazoline phosphate surfactant aqueous solution, wherein the conversion rate of the oleic acid lauric acid based imidazoline intermediate is 95.1%.
Asymmetric oleic acid lauric acid radical geminiThe IR spectrum of the oxazoline phosphate surfactant is shown in figure 1, wherein the spectrum is 2924cm-1The vibration absorption peak of C-H is nearby; 2854cm-1Is nearby CH2Symmetric stretching vibration of the middle C-H bond; 1644cm-1The nearby absorption peak is a C ═ O characteristic absorption peak; 1462cm-1Is nearby CH2Symmetric stretching vibration of the middle C-H bond; 1043cm-1The vicinity is a characteristic absorption peak of hydroxyl; 934cm-1The vicinity is a P-O-C bending vibration absorption peak. The characteristics of the functional groups are consistent with the structure of the product, which shows that the asymmetric oleic acid lauric acid based gemini imidazoline phosphate surfactant is successfully synthesized.
Example 2
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.03 mol and 106.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding oleic acid (1 mol and 282.5 g) and phosphoric acid (1.1 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 15000pa, heating to 140 ℃, reacting for 3h, adding n-capric acid (1 mol and 172.3 g), heating at 20 ℃/h in a gradient manner to 170 ℃ for reacting for 4h, heating to 240 ℃ for cyclization reaction, evaporating until no water is removed after 4h, cooling to 80 ℃, obtaining 504.5 g of oleic acid decanoyl imidazoline intermediate, and measuring the acid value to be 2.2mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
ammonium dihydrogen phosphate (0.36 mol, 41.4 g) was dissolved in 302.8 g of water in a 1 l four-necked flask equipped with an electric stirrer, a thermometer and a condenser, and then heated to 80 ℃ under stirring, epichlorohydrin (0.3 mol, 27.8 g) was added under reflux condensation to react for 3.5 hours, and then the conversion of epichlorohydrin was determined to be 99.1%, thereby obtaining a transparent ammonium 3-chloro-2-hydroxypropanoate aqueous solution.
Step three, alkylation reaction:
adding the oleic acid decanoic acid base imidazoline intermediate (0.15 mol and 75.6 g) and the monoethanolamine (0.3 mol and 18.3 g) prepared in the first step into the transparent 3-chloro-2-hydroxy propyl ammonium phosphate (0.3 mol) aqueous solution prepared in the second step, stirring and heating to 80 ℃, and reacting for 4 hours to obtain the asymmetric oleic acid decanoic acid base gemini imidazoline phosphate surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 95.2%.
Example 3
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.03 mol and 106.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding oleic acid (1 mol and 282.5 g) and phosphoric acid (1.1 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 20000pa, heating to 140 ℃, reacting for 3h, adding n-octanoic acid (1 mol and 144.2 g), heating to 170 ℃ in a gradient manner at 20 ℃/h, reacting for 3h, heating to 230 ℃ for cyclization reaction until water is evaporated out after 4h, cooling to 80 ℃, obtaining an octocaprylic imidazoline oleate intermediate 476.2 g, and measuring the acid value to be 2.3mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle provided with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.36 mol, 41.4 g) is dissolved in 344.1 g of water, the temperature is raised to 75 ℃ by stirring, epichlorohydrin (0.3 mol, 27.8 g) is added for reaction for 4 hours under the state of condensation reflux, the conversion rate of the epichlorohydrin is determined to be 98.8 percent, and the transparent 3-chloro-2 hydroxyl propyl ammonium phosphate aqueous solution is obtained.
Step three, alkylation reaction:
adding the oleic acid octanoic acid base imidazoline intermediate (0.15 mol, 71.4 g) and triethanolamine (0.3 mol, 44.8 g) prepared in the first step into the transparent 3-chloro-2-hydroxy propyl ammonium phosphate (0.3 mol) aqueous solution prepared in the second step, stirring and heating to 75 ℃, and reacting for 4h to obtain the asymmetric oleic acid octanoic acid base gemini imidazoline phosphate salt surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 94.8%.
Example 4
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding linoleic acid (1 mol and 280.4 g) and phosphoric acid (1.2 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 13000pa, heating to 140 ℃, reacting for 3h, adding lauric acid (1 mol and 200.3 g), heating to 170 ℃ at a gradient of 20 ℃/h, reacting for 4h, heating to 250 ℃ for cyclization reaction until no water is evaporated after 4h, cooling to 80 ℃, obtaining a linoleic acid lauroyl imidazoline intermediate 530.3 g, and measuring the acid value to be 2.3mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle provided with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.33 mol and 38.0 g) is dissolved in 262.1 g of water, the temperature is raised to 85 ℃ by stirring, epichlorohydrin (0.3 mol and 27.8 g) is added for reaction for 3.5 hours under the state of condensation reflux, the conversion rate of the epichlorohydrin is determined to be 99.2 percent, and the transparent 3-chloro-2 hydroxyl ammonium phosphate aqueous solution is obtained.
Step three, alkylation reaction:
adding the oleic acid lauric acid base imidazoline intermediate (0.15 mol and 79.5 g) prepared in the first step and ammonia water (0.3 mol and 37.5 g) with the mass concentration of 28% into the transparent 3-chloro-2-hydroxypropionic acid ammonium phosphate (0.3 mol) aqueous solution prepared in the second step, stirring and heating to 85 ℃, and reacting for 4 hours to obtain the asymmetric linoleic acid lauric acid base gemini imidazoline phosphate surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 95.6%.
Example 5
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding linoleic acid (1 mol and 280.4 g) and phosphoric acid (1.1 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 15000pa, heating to 140 ℃, reacting for 3h, adding n-capric acid (1 mol and 172.3 g), heating at 20 ℃/h in a gradient manner to 170 ℃ for reacting for 4h, heating to 240 ℃ for cyclization reaction until water is evaporated after 4h, cooling to 80 ℃, obtaining 502.5 g of linoleic acid decanoyl imidazoline intermediate, and measuring the acid value to be 1.6mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle equipped with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.33 mol, 38.0 g) was dissolved in 262.1 g of water, the temperature was raised to 80 ℃ under stirring, epichlorohydrin (0.3 mol, 27.8 g) was added under a condensation reflux state for reaction for 3.5 hours, and the conversion of epichlorohydrin was determined to be 98.5%, to obtain a transparent ammonium 3-chloro-2-hydroxypropanoate aqueous solution.
Step three, alkylation reaction:
adding 0.15 mol and 75.3 g of linoleic acid decanoyl imidazoline intermediate and 0.3 mol and 18.3 g of monoethanolamine prepared in the first step into the transparent 0.3 mol of 3-chloro-2-hydroxypropionic phosphate ammonium aqueous solution prepared in the second step, stirring and heating to 80 ℃, and reacting for 4h to obtain an asymmetric linoleic acid decanoyl gemini imidazoline phosphate surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 95.8%.
Example 6
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding linoleic acid (1 mol and 280.4 g) and phosphoric acid (1.1 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 20000pa, heating to 140 ℃, reacting for 3h, adding n-octanoic acid (1 mol and 144.2 g), heating to 170 ℃ in a gradient manner at 20 ℃/h, reacting for 4h, heating to 240 ℃ for cyclization reaction until no water is evaporated after 4h, cooling to 80 ℃ to obtain an linolic acid octanoic acid imidazoline intermediate 474.8 g, and measuring the acid value to be 1.2mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle provided with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.25 mol, 28.5 g) is dissolved in 285.9 g of water, the temperature is raised to 75 ℃ by stirring, epichlorohydrin (0.225 mol, 20.8 g) is added for reaction for 4 hours under the state of condensation reflux, the conversion rate of the epichlorohydrin is determined to be 98.3 percent, and transparent 3-chloro-2 hydroxyl propyl ammonium phosphate aqueous solution is obtained.
Step three, alkylation reaction:
adding 0.15 mol and 71.1 g of linoleoic acid octanoyl imidazoline intermediate and 0.225 mol and 33.6 g of triethanolamine into the transparent 0.225 mol of ammonium 3-chloro-2-hydroxypropionate prepared in the second step, stirring and heating to 75 ℃, and reacting for 5 hours to obtain the asymmetric linoleoic acid octanoyl gemini imidazoline phosphate salt surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 96.3%.
Example 7
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding myristic acid (1 mol and 228.4 g) and phosphoric acid (1.0 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 15000pa, heating to 140 ℃, reacting for 3h, adding n-capric acid (1 mol and 172.3 g), heating at 20 ℃/h in a gradient manner to 170 ℃ for reacting for 4h, heating to 230 ℃ for cyclization reaction, evaporating until no water is removed after 4h, cooling to 80 ℃, obtaining myristic decanoic acid imidazoline intermediate 450.3 g, and measuring the acid value to be 1.5mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle provided with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.25 mol and 28.5 g) is dissolved in 211.1 g of water, the temperature is raised to 80 ℃ by stirring, epichlorohydrin (0.225 mol and 20.8 g) is added for reaction for 3.5 hours under the state of condensation reflux, the conversion rate of the epichlorohydrin is determined to be 99.2 percent, and the transparent 3-chloro-2-hydroxyl propyl ammonium phosphate aqueous solution is obtained.
Step three, alkylation reaction:
adding the myristic acid decanoyl imidazoline intermediate (0.15 mol and 67.5 g) and ammonia water (0.225 mol and 28.2 g) with the mass concentration of 28% into the transparent 3-chloro-2-hydroxypropionic acid ammonium phosphate (0.225 mol) aqueous solution prepared in the second step, stirring and heating to 80 ℃, and reacting for 4 hours to obtain the asymmetric myristic acid decanoyl bisimidazoline phosphate salt surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 97.0%.
Example 8
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding myristic acid (1 mol and 228.4 g) and phosphoric acid (1.0 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 20000pa, heating to 140 ℃, reacting for 3h, adding n-octanoic acid (1 mol and 144.2 g), heating at a gradient of 20 ℃/h to 170 ℃ for reacting for 4h, heating to 230 ℃ for cyclization reaction until anhydrous is evaporated after 3.5h, cooling to 80 ℃ to obtain 422.6 g of myristic acid octanoyl imidazoline intermediate, and measuring the acid value to be 0.98mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
ammonium dihydrogen phosphate (0.25 mol, 28.5 g) was dissolved in 234.5 g of water in a 1 l four-necked flask equipped with an electric stirrer, a thermometer and a condenser, and then heated to 75 ℃ under stirring, epichlorohydrin (0.225 mol, 20.8 g) was added under reflux condensation to react for 4.5 hours, and the conversion of epichlorohydrin was determined to be 98.7%, thereby obtaining a transparent aqueous solution of ammonium 3-chloro-2-hydroxypropionate.
Step three, alkylation reaction:
adding 0.15 mol and 63.3 g of the myristic acid octanoyl imidazoline intermediate and 0.225 mol and 13.7 g of monoethanolamine into the transparent 0.225 mol aqueous solution of the 3-chloro-2-hydroxypropionic acid ammonium phosphate prepared in the second step, stirring and heating to 75 ℃, and reacting for 5 hours to obtain the asymmetric myristic acid octanoyl gemini imidazoline phosphate salt surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 97.4%.
Example 9
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding lauric acid (1 mol and 228.4 g) and phosphoric acid (1.0 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 15000pa, heating to 140 ℃, reacting for 2h, adding n-capric acid (1 mol and 172.3 g), heating to 170 ℃ at a gradient of 20 ℃/h, reacting for 3h, heating to 220 ℃ for cyclization reaction until water is evaporated after 3h, cooling to 80 ℃ to obtain a lauric acid decanoyl imidazoline intermediate 422.3 g, and measuring the acid value to be 0.73mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
in a 1L four-mouth bottle provided with an electric stirrer, a thermometer and a condenser, ammonium dihydrogen phosphate (0.224 mol and 25.8 g) is dissolved in 194.0 g of water, the temperature is raised to 80 ℃ by stirring, epichlorohydrin (0.195 mol and 18.0 g) is added for reaction for 3.5 hours under the state of condensation reflux, the conversion rate of the epichlorohydrin is determined to be 98.9 percent, and the transparent 3-chloro-2-hydroxyl propyl ammonium phosphate aqueous solution is obtained.
Step three, alkylation reaction:
adding the lauric acid decanoic acid radical imidazoline intermediate (0.15 mol and 63.3 g) and the monoethanolamine (0.194 mol and 6.8 g) prepared in the first step into the transparent 3-chloro-2-hydroxypropionic acid ammonium phosphate (0.195 mol) aqueous solution prepared in the second step, stirring and heating to 80 ℃, and reacting for 5 hours to obtain the asymmetric lauric acid decanoic acid radical gemini imidazoline phosphate salt surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 97.0%.
Example 10
Step one, synthesizing an asymmetric gemini imidazoline intermediate:
adding diethylenetriamine (1.05 mol and 108.3 g) into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding lauric acid (1 mol and 228.4 g) and phosphoric acid (1.0 g) under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum negative pressure of a reaction system to 20000pa, heating to 140 ℃, reacting for 2h, adding n-octanoic acid (1 mol and 144.2 g), heating to 170 ℃ in a gradient manner at 20 ℃/h, reacting for 3h, heating to 220 ℃ for cyclization reaction, evaporating until no water is removed after 2h, cooling to 80 ℃ to obtain an intermediate 394.3 g of caprylic laurate imidazoline, and measuring the acid value to be 0.58mg KOH/g.
Secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
ammonium dihydrogen phosphate (0.224 mol, 25.8 g) was dissolved in 245.1 g of water in a 1 l four-neck flask equipped with an electric stirrer, a thermometer and a condenser, and then heated to 75 ℃ under stirring, and then epichlorohydrin (0.195 mol, 18.0 g) was added under reflux condensation to react for 4.5 hours, and the conversion of epichlorohydrin was determined to be 98.5%, thereby obtaining a transparent 3-chloro-2-hydroxypropanoate ammonium aqueous solution.
Step three, alkylation reaction:
adding 0.15 mol and 59.1 g of lauric acid caprylic acid imidazoline intermediate and 0.194 mol and 29.1 g of triethanolamine into the transparent 0.195 mol of ammonium 3-chloro-2-hydroxypropionate prepared in the second step, stirring and heating to 75 ℃, and reacting for 5 hours to obtain the asymmetrical lauric acid caprylic acid gemini imidazoline phosphate salt surfactant aqueous solution, wherein the conversion rate of the imidazoline intermediate is 97.4%.
Comparative example 1
The alkylation was carried out using sodium hydroxide as a catalyst, and the procedure of comparative example was otherwise the same as in example 1.
Comparative example 2
The alkylation was carried out using 3-chloro-2-ylpropanesulfonate in place of 3-chloro-2-hydroxypropanolammonium phosphate, as in example 1.
Example 11
Test of corrosion inhibition performance of asymmetric gemini imidazoline phosphate surfactant
Static weightlessness is adopted to test the corrosion inhibition performance of the asymmetric gemini imidazoline phosphate surfactant in an acid system, and the experimental method comprises the following steps:
a is to be3Carbon steel test piece (specification is 50mm multiplied by 25mm multiplied by 2mm, surface area is 28cm2) Respectively immersing the steel plates into 500mL of hydrochloric acid aqueous solution with the mass fractions of 4% and the corrosion inhibitors of 100mg/L, 200mg/L, 300mg/L, 400mg/L and 500mg/L, standing for 4h, taking out, washing, drying, weighing and calculating the corrosion inhibition rate.
At 90 ℃, as shown in table 1, table 1 is the relationship between the concentration of the asymmetric oleic lauric acid based gemini imidazoline phosphate surfactant prepared in example 1 and the corrosion inhibition rate. With the increase of the concentration of the asymmetrical oleic acid lauric acid based gemini imidazoline phosphate surfactant, the corrosion inhibition rate is gradually improved, the concentration is increased to 300mg/L, and the A is treated3The corrosion inhibition rate of the carbon steel sheet is 93.4%, and the carbon steel sheet has a good corrosion inhibition effect on carbon steel. Comparative example 1 asymmetric oleic acid lauric acid based gemini imidazoline phosphate salt was synthesized in the same manner as in example 1 with sodium hydroxide as catalyst in alkylation, and the corrosion inhibition performance was significantly inferior to that of example 1 using ammonia as catalyst. Synthesis of asymmetric oleic acid lauric acid based gemini imidazoline phosphate salt of p-A in acidic System by substituting 3-chloro-2-yl propanesulfonate for 3-chloro-2-hydroxypropanolammonium phosphate in alkylation of p-proportion 2 in the same manner as in example 13The carbon steel sheet has poor corrosion inhibition rate.
According to the asymmetrical gemini imidazoline phosphate surfactant provided by the invention, organic base is used for replacing inorganic base, 3-chloro-2-hydroxyl ammonium propionate is not easy to hydrolyze during alkylation, the obtained asymmetrical gemini imidazoline phosphate surfactant has good water solubility and more excellent corrosion inhibition performance on metal, the used raw materials are safe and environment-friendly, the reaction process is simple, the yield and the atom utilization rate are high, the industrial large-scale production is suitable, the environment-friendly gemini imidazoline phosphate surfactant accords with the green development direction of the current anticorrosion technology, and the development and innovation of the anticorrosion technology in China are powerfully promoted.
TABLE 1 Corrosion inhibition Performance test
Figure BDA0003173200120000121
The surfactants obtained in the above examples were subjected to performance tests, and the results are shown in table 2.
The test of the wetting time of the asymmetric gemini imidazoline phosphate surfactant is carried out by referring to corresponding national standards (a method for measuring the wetting force of the surfactant GB/T11983-: preparing 1000mL of aqueous solution with the effective content of 1% by adopting a standard canvas sheet settling method, flatly placing the standard canvas sheet on the surface of the aqueous solution of the surfactant at a constant temperature of 25.0 +/-0.5 ℃, starting timing, stopping timing when the canvas sheet begins to sink from the liquid surface, repeating the operation for ten times for each sample, taking an average value as the wetting time of the surfactant or the composition, wherein the shorter the time, the better the wetting property is.
The invention discloses a method for testing the emulsibility of an asymmetric gemini imidazoline phosphate surfactant, which comprises the following steps: adding 40mL of tallowimidazoline biquaternary ammonium salt surfactant with the mass fraction of 0.50% and 40mL of soybean oil into a measuring cylinder, violently shaking up and down for 10 times, placing on a horizontal plane for timing, recording the time required for 10mL of water to be separated out, and taking the arithmetic average value of 5 times as the emulsibility test result of the tallowimidazoline sulfonate.
The surface tension (mN/m) and the critical micelle concentration (mg/L) of the asymmetric gemini imidazoline phosphate surfactant are tested according to GB/T22237-2008. Preparing tall oil acid imidazoline sulfonate aqueous solution with a series of concentrations, carrying out surface tension test on Kruss-K100 at 25 +/-0.1 ℃, then drawing a curve of surface tension changing along with concentration, and determining the surface tension gamma cmc and the critical micelle concentration cmc according to the inflection point of the surface tension changing along with the logarithmic curve of the concentration.
TABLE 2
Figure BDA0003173200120000122
Figure BDA0003173200120000131
As can be seen from the data in table 2, the critical micelle concentration cmc of the asymmetric gemini imidazoline phosphate surfactants obtained in example 1 and example 2 is lower, the wettability is better, and the emulsifying performance is more excellent.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A preparation method of an asymmetric gemini imidazoline phosphate surfactant is characterized by comprising the following steps:
step one, synthesizing an asymmetric gemini imidazoline intermediate:
under the protection of nitrogen, adding C8～C18Mixing fatty acid, organic polyamine and phosphoric acid, heating to 100-200 ℃ under the vacuum negative pressure of 1500-30000 Pa, reacting for 2-10 h, and adding C12～C18Heating the fatty acid to 130-250 ℃ in a gradient manner, reacting for 1-8 h, heating to 220-250 ℃ for cyclization reaction until no water is evaporated out, and obtaining an asymmetric gemini imidazoline intermediate;
the phosphoric acid accounts for C8～C18Fatty acids, organic polyamines, C12～C18The mass percentage of the total mass of the fatty acid and the phosphoric acid is 0.01-1%;
said C is8～C18Fatty acid, C12～C18The molar ratio of the fatty acid to the organic polyamine is (0.9-1.1): (0.9-1.1): (0.3 to 1.5);
the organic polyamine is at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
said C is8～C18The fatty acid is one of oleic acid, linoleic acid, myristic acid and lauric acid;
said C is12～C18The fatty acid is one of lauric acid, n-capric acid and n-caprylic acid;
said C is8～C18Fatty acids with said C12～C18The fatty acid is not the same fatty acid at the same time;
secondly, synthesizing 3-chloro-2-hydroxyl propyl phosphate ammonium aqueous solution:
dissolving ammonium dihydrogen phosphate in water, wherein the mass ratio of the ammonium dihydrogen phosphate to the water is 1 (5-20), stirring and heating to 60-100 ℃, and dropwise adding epoxy chloropropane for reacting for 1-6 hours under the condition of condensation reflux to obtain a transparent 3-chloro-2-hydroxypropyl ammonium phosphate aqueous solution;
the molar ratio of the ammonium dihydrogen phosphate to the epoxy chloropropane is (1-2) to 1;
step three, alkylation reaction:
adding the asymmetric gemini imidazoline intermediate and the organic base obtained in the first step into the transparent 3-chloro-2-hydroxypropionate ammonium aqueous solution in the second step, stirring and heating to 50-95 ℃, and reacting for 1-10 h to obtain an asymmetric gemini imidazoline phosphate surfactant;
the molar ratio of the asymmetric gemini imidazoline intermediate, the 3-chlorine-2 hydroxyl propyl ammonium phosphate and the organic alkali is 1 (1.1-3) to 0.5-3;
the organic alkali is ammonia water, monoethanolamine, diethanolamine or triethanolamine.
2. The method for preparing the unsymmetrical gemini imidazoline phosphate ester surfactant according to claim 1, wherein in the first step, the acid value of the unsymmetrical gemini imidazoline intermediate is 0.2-3 mg KOH/g.
3. The method for preparing the asymmetric gemini imidazoline phosphate ester surfactant according to claim 1, wherein in the first step, the gradient temperature rise is performed at a temperature rise rate of 5-25 ℃/h.
4. The process for preparing the unsymmetrical gemini imidazoline phosphate salt surfactant of claim 1, wherein in the first step, phosphoric acid is C8～C18Fatty acids, organic polyamines, C12～C18The mass percentage of the total mass of the fatty acid and the phosphoric acid was 0.2%.
5. The process for preparing unsymmetrical gemini imidazoline phosphate ester surfactants according to claim 1, wherein in the first step, C is8～C18Fatty acid, C12～C18The molar ratio of the fatty acid to the organic polyamine is 1:1 (1.01-1.1).
6. The process for preparing the unsymmetrical gemini imidazoline phosphate ester salt surfactant according to claim 1, wherein in the first step, the organic polyamine is diethylenetriamine.
7. The method for preparing the asymmetrical gemini imidazoline phosphate surfactant according to claim 1, wherein in the second step, the molar ratio of ammonium dihydrogen phosphate to epichlorohydrin is (1.1-1.2): 1.
8. The method for preparing the asymmetric gemini imidazoline phosphate surfactant according to claim 1, wherein in the third step, the molar ratio of the asymmetric gemini imidazoline intermediate, the 3-chloro-2-hydroxypropanoate ammonium salt and the organic base is 1 (1.1-3) to 1.1-2.
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