CN108440323B - Star-shaped multi-cation-based surfactant and preparation method and application thereof - Google Patents

Star-shaped multi-cation-based surfactant and preparation method and application thereof Download PDF

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CN108440323B
CN108440323B CN201810274280.3A CN201810274280A CN108440323B CN 108440323 B CN108440323 B CN 108440323B CN 201810274280 A CN201810274280 A CN 201810274280A CN 108440323 B CN108440323 B CN 108440323B
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王晨
王霞
辛燕
杨晓武
费贵强
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Abstract

The invention discloses a star multi-cation surfactant as well as a preparation method and application thereof, wherein the surfactant is prepared by the following steps: dropwise adding quantitative trimethylolpropane-tri (3-aziridinyl propionate) reaction liquid into a reaction bottle filled with long-chain aliphatic primary amine ethanol solution and an acid catalyst to perform a first step of aziridine ring opening reaction; then adding quantitative chloromethane (or benzyl chloride) reaction liquid into the reaction liquid to carry out second-step quaternization reaction, and obtaining a star-shaped multi-cation surfactant.

Description

Star-shaped multi-cation-based surfactant and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of multi-quaternary ammonium salt cationic surfactants, in particular to a star multi-cationic surfactant and a preparation method and application thereof.
Background
The multi-cation quaternary ammonium salt surfactant has a plurality of hydrophilic groups and a plurality of hydrophobic groups, so that the multi-cation quaternary ammonium salt surfactant has higher surface/interface activity, lower critical micelle concentration, better bactericidal performance, good foaming power and foam stability, unique rheological property and other physicochemical properties, and is widely applied to the fields of preparing new materials and bactericides, inhibiting metal corrosion, dyeing and finishing fabrics, petroleum exploitation and the like. At present, the most widely researched polycationic quaternary ammonium salt surfactant is a cationic gemini surfactant, but a star-shaped polycationic surfactant is not provided to meet the existing requirement.
With the development of petroleum engineering technology, drilling operations of deep wells, extended reach wells, horizontal wells and the like are increased, the drilling of stratums is more and more complex, and part of high-difficulty oil wells have the characteristics of large well bores, large displacement, long horizontal well section, large change of well bore tracks and the like, so that the problems of serious collapse, expansion and shrinkage, serious slurry making and the like of shale stratums are caused, the higher requirement on the inhibition capacity of the water-based drilling fluid is provided, and the efficient clay stabilizer is the key for ensuring the stability of well walls and the inhibition capacity of the drilling fluid. In recent years, small molecular quaternary ammonium salt clay stabilizer is gradually valued, and is easily preferentially adsorbed by clay, so that dehydration among clay crystal layers can be promoted, the expansive force is reduced, the hydration of the clay is effectively inhibited, and the clay crystal layers can be embedded to prevent water molecules from entering, the hydration and expansion effects of the clay are reduced, and the small molecular quaternary ammonium salt clay stabilizer has a long-term stable effect due to firm adsorption on clay particles. However, the existing quaternary ammonium salt clay stabilizer has the problems of large dosage, low anti-swelling rate, large damage to stratum and the like, and the invention redesigns the molecular structure of the quaternary ammonium salt clay stabilizer to synthesize the high-performance star-shaped multi-quaternary ammonium salt clay stabilizer. The clay stabilizer can effectively inhibit hydration expansion and dispersion migration of clay under extremely low dosage.
Disclosure of Invention
In order to expand the variety of the multi-cation quaternary ammonium salt surfactant and the quantity of the multi-cation quaternary ammonium salt, the invention uses the reaction of the high-activity aziridine crosslinking agent and the active amine group to form an independent star structure, and then introduces the alkyl halide to carry out quaternization reaction, thereby obtaining the multi-cation surfactant with the star structure. One of the purposes of the invention is to provide a star-shaped multi-cation surfactant.
The second purpose of the invention is to provide a preparation method of the surfactant.
In order to achieve the purpose, the invention adopts the following technical scheme:
a star-shaped multi-cation surfactant has a structural formula as follows:
Figure GDA0002763308010000021
wherein R is1-is a long aliphatic chain with 12-18 carbon atoms in the carbon chain; r2-is-H or
Figure GDA0002763308010000022
A preparation method of a star-shaped multi-cation surfactant comprises the following steps:
adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into a long-chain fatty primary amine ethanol solution and an acid catalyst to perform aziridine ring-opening reaction, and reacting at 50-80 ℃ for 6-8 h;
under the alkalescent condition, adding methyl chloride or benzyl chloride reaction liquid into the reactant to carry out quaternization reaction, and reacting for 10-16 h at 50-70 ℃ under the protection of nitrogen; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
In the aziridine ring opening reaction, the molar ratio of trimethylolpropane-tris (3-aziridinylpropionate) and long chain fatty primary amine was 1: 3.
In the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.
In the quaternization reaction, the pH value is 9-10 under the alkalescent condition, and K is used for reaction liquid2CO3And adjusting to alkalescence.
In the quaternization reaction, the amount of methyl chloride or benzyl chloride material is 6 times that of trimethylolpropane-tris (3-aziridinylpropionate).
An application of a star-shaped multi-cation surfactant as a clay stabilizer in oil and gas exploitation.
The addition amount of the clay stabilizer is 0.2-1% of the total mass.
Compared with the prior art, the invention has the following advantages:
the star polycation-based surfactant contains eighteen quaternary ammonium salt groups, can simultaneously act on negatively charged clay particle surfaces in multiple points, has a wide action range, and can be used as an efficient clay stabilizer.
According to the invention, a star-shaped surfactant carrying active secondary amine is formed by reacting a high-activity aziridine crosslinking agent with active amine groups, and a quaternary ammonium salt reagent carrying quaternary ammonium salt is introduced for reaction to obtain the star-shaped multi-cation surfactant, so as to expand the variety of the multi-cation quaternary ammonium salt surfactant and the number of the multi-cation quaternary ammonium salts.
The invention redesigns the molecular structure of the quaternary ammonium salt clay stabilizer to synthesize the high-performance star-shaped multi-quaternary ammonium salt clay stabilizer. The clay stabilizer can effectively inhibit hydration expansion and dispersion migration of clay under extremely low dosage. The multi-cation-group star clay stabilizer can simultaneously act on negatively charged clay particles at multiple points due to the fact that the molecules contain a plurality of quaternary ammonium salt groups, and is high in adsorption degree, so that the purposes of low dosage and high anti-swelling rate are achieved.
Drawings
FIG. 1 is a chemical structural formula of the present invention;
FIG. 2 is a scheme of the synthesis of the reaction of the present invention.
Detailed Description
As shown in fig. 1 and 2, the reaction equation of the present invention is:
Figure GDA0002763308010000041
wherein R is1-is a long aliphatic chain with 12-18 carbon atoms in the carbon chain; r2-is-H or
Figure GDA0002763308010000042
According to the reaction mechanism, the structural formula of the star multi-cation surfactant is as follows:
Figure GDA0002763308010000043
wherein R is1-is a long aliphatic chain with 12 to c carbon atoms in the carbon chain18；R2-is-H or
Figure GDA0002763308010000044
The method for preparing the star multi-cation surfactant comprises the following steps:
dropwise adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into a reaction bottle filled with a long-chain fatty primary amine ethanol solution and an acid catalyst to perform a first-step aziridine ring-opening reaction, wherein the molar ratio of the trimethylolpropane-tris (3-aziridinyl propionate) to the long-chain fatty primary amine is 1:3, and reacting at 50-70 ℃ for 6-8 h; then using K to react the reaction solution2CO3And (3) adjusting the pH value to be alkalescent (9-10), adding methyl chloride (or benzyl chloride) reaction liquid to perform a second-step quaternization reaction, wherein the amount of the methyl chloride (or benzyl chloride) is 6 times of that of trimethylolpropane-tris (3-aziridinyl propionate), and reacting at 50-70 ℃ for 10-16 h under the protection of nitrogen. Removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) In a mixture of an 80% ethanol solution (34.69g, containing 27.75g, 0.15mol of primary dodecylamine) of a primary dodecylamine and an acidic catalyst (85% H)3PO40.50g), heated to 50 ℃, and then 70 percent by mass of trimethylolpropane-tris (3-aziridinyl propionate) ethanol solution (35.42g, which contains 21.25g of trimethylolpropane-tris (3-aziridinyl propionate) and 0.05mol) is added dropwise for 40 min. After the dropwise addition, the temperature is raised to 70 ℃ for reaction for 6 hours.
(2) Using K as the reaction solution2CO3Adjusted to weak baseDropwise adding a chloromethane ethanol solution (25.25g, wherein the chloromethane is 15.15g and 0.30mol) with the mass fraction of 60% under the protection of nitrogen, and reacting at 50 ℃ for 10 hours; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum to constant weight to obtain the product.
The structural formula of the product obtained in example 1 is:
Figure GDA0002763308010000061
1H NMR(300MHz，DMSO)：3.94(s，6H)，3.63～3.68(m，18H)，3.30(s，36H)，3.22(t，6H)，2.69(t，6H)，1.68～1.71(m，8H)，1.26～1.29(s，54H)，0.83～0.88(m，12H)ppm。
13C NMR(300MHz，DMSO)：173.1，65.9，64.4，61.8，58.8～59.1，52.0～52.3，35.7，31.9，29.3～29.6，26.8，25.4，22.7，14.1，7.3ppm。
example 2
(1) In a reaction vessel containing 80% by mass of an ethanol solution of primary octadecylamine (50.53g, containing 40.43g, 0.15mol of primary octadecylamine) and an acidic catalyst (85% H)3PO40.60g), heated to 50 ℃, and then 70 percent by mass of trimethylolpropane-tris (3-aziridinyl propionate) ethanol solution (35.42g, which contains 21.25g of trimethylolpropane-tris (3-aziridinyl propionate) and 0.05mol) is added dropwise for 40 min. After the dropwise addition, the temperature is raised to 50 ℃ for reaction for 8 hours.
(2) Using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding 80% benzyl chloride ethanol solution (47.48g, wherein 37.98g of benzyl chloride is contained, 0.30mol) under the protection of nitrogen, and reacting at 70 ℃ for 16 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
The structural formula of the product obtained in example 2 is:
Figure GDA0002763308010000071
1H NMR(300MHz，DMSO)：7.16～7.25(m，60H)，4.5(s，24H)，3.63～3.68(m，18H)，3.22(t，6H)，2.69(t，6H)，1.69～1.71(m，8H)，1.26～1.29(s，90H)，0.83(t，12H)ppm。
13C NMR(300MHz，DMSO)：173.1，125.7～131.6，65.9，60.8～54.6，35.7，22.7～31.9，14.1，7.1ppm。
example 3
(3) In a solution of 80% by mass of an ethanol solution of a primary tetradecyl amine (40.03g, containing 32.03g of a primary tetradecyl amine, 0.15mol) and an acidic catalyst (85% H)3PO40.50g), heated to 50 ℃, and then 70 percent by mass of trimethylolpropane-tris (3-aziridinyl propionate) ethanol solution (35.42g, which contains 21.25g of trimethylolpropane-tris (3-aziridinyl propionate) and 0.05mol) is added dropwise for 40 min. After the dropwise addition, the temperature is raised to 60 ℃ for reaction for 7 hours.
(4) Using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding 80% benzyl chloride ethanol solution (47.48g, wherein 37.98g of benzyl chloride is contained, 0.30mol) under the protection of nitrogen, and reacting at 60 ℃ for 12 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
The structural formula of the product obtained in example 3 is:
Figure GDA0002763308010000081
example 4
(1) In a solution containing 80% by mass of an ethanol solution of primary hexadecylamine (45.29g, containing 36.23g, 0.15mol of primary hexadecylamine) and an acidic catalyst (85% H)3PO40.50g), heating to 50 ℃, and dropwise adding 70 percent of trimethylolpropane-tri (3-aziridinylpropane)Acid ester) ethanol solution (35.42g, containing trimethylolpropane-tris (3-aziridinylpropionate) 21.25g, 0.05mol), was added dropwise over a period of 40 min. After the dropwise addition, the temperature is raised to 60 ℃ for reaction for 7 hours.
(2) Using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding a chloromethane ethanol solution (25.25g, wherein the chloromethane is 15.15g and 0.30mol) with the mass fraction of 60% under the protection of nitrogen, and reacting at 60 ℃ for 12 hours; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum to constant weight to obtain the product.
The structural formula of the product obtained in example 4 is:
Figure GDA0002763308010000082
characterization of Clay stabilizer Properties
(1) Clay stabilizer swelling resistance and washing resistance test
The expansion prevention rate is evaluated by measuring the expansion increment of the sodium bentonite in a clay stabilizer solution and distilled water according to a centrifugal method in a standard SY/T5971-2016 clay stabilizer performance evaluation method for oil and gas field fracturing acidification and water injection and Q/SH 0053-2010 clay stabilizer technical requirement. The clay stabilizers of examples 1 to 3 were measured for their anti-swelling rate and water washing resistance in water. The results are shown in Table 1.
TABLE 1 Clay stabilizer swell prevention and Water washing resistance
Figure GDA0002763308010000091
As can be seen from the table, the clay stabilizer of the invention has the anti-swelling rate higher than 80% and the water washing resistance rate higher than 90% in the clear water fracturing fluid under the addition of 0.2%; the clay stabilizer has the anti-swelling rate higher than 90% in the clear water fracturing fluid under the addition of 0.5%; the clay stabilizer has the anti-swelling rate higher than 93% in the clear water fracturing fluid under the addition of 1.0%. The clay stabilizers (potassium chloride and ammonium chloride) of the control inorganic salts showed less than 70% anti-swelling at 2.0% addition.
(2) Compatibility test
The results of the compatibility observation of the clay stabilizers of examples 1 to 3 with the base fluid and the acid solution of the fracturing fluid are shown in table 2.
TABLE 2 compatibility test of Clay stabilizers
Figure GDA0002763308010000101
As can be seen from Table 2, the clay stabilizer of the present invention has no delamination, sedimentation and suspension phenomena when mixed with a fracturing fluid base and an acid solution, and has good compatibility.
Example 5
(1) In a reactor containing 20% by mass of methylamine water solution (23.25g, containing 4.65g, 0.15mol of methylamine) and acidic catalyst (85% H)3PO40.30g), heated to 40 ℃, and then added dropwise with a 70% by mass fraction aqueous solution (35.42g, containing 21.25g, 0.05mol of trimethylolpropane-tris (3-aziridinyl propionate) over 40 min. After the dropwise addition, the temperature is raised to 70 ℃ for reaction for 5 hours.
(2) Using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding a chloromethane ethanol solution (25.25g, wherein the chloromethane is 15.15g and 0.30mol) with the mass fraction of 60% under the protection of nitrogen, and reacting at 50 ℃ for 10 hours; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum to constant weight to obtain the product.
The structural formula of the product obtained in example 5 is:
Figure GDA0002763308010000111
1H NMR(300MHz，DMSO)：3.91(s，6H)，3.67(m，18H)，3.26(m，33H)，2.70(t，6H)，1.67(m，2H)，1.27(t，36H)，0.84(t，3H)ppm。
13C NMR(300MHz，DMSO)：173.5，66.1，54.1～56.8，49.5，35.7，27.3，23.0，7.9～8.3ppm。
example 6
(1) In a 70% ethylamine water solution (9.54g, containing 6.75g of ethylamine and 0.15mol) and an acid catalyst (85% H)3PO40.30g), heated to 50 ℃, and then added dropwise with a 70% by mass fraction aqueous solution (35.42g, containing 21.25g, 0.05mol of trimethylolpropane-tris (3-aziridinyl propionate) over 40 min. After the dropwise addition, the temperature is raised to 70 ℃ for reaction for 7 hours.
(2) Using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding 80% benzyl chloride ethanol solution (47.48g, wherein 37.98g of benzyl chloride is contained, 0.30mol) under the protection of nitrogen, and reacting at 70 ℃ for 16 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
The structural formula of the product obtained in example 6 is:
Figure GDA0002763308010000121
1H NMR(300MHz，DMSO)：7.16～7.25(m，60H)，4.50(s，24H)，3.94(s，6H)，3.63～3.68(m，18H)，3.28(m，6H)，2.70(t，6H)，1.69(m，2H)，1.25(t，12H),0.83(t，3H)ppm。
13C NMR(300MHz，DMSO)：173.1，125.3～131.6，65.9，60.4，54.2～56.6，35.7，27.3，23.0，7.7～8.3ppm。
characterization of Clay stabilizer Properties
(1) Clay stabilizer swelling resistance and washing resistance test
The expansion prevention rate is evaluated by measuring the expansion increment of the sodium bentonite in a clay stabilizer solution and distilled water according to a centrifugal method in a standard SY/T5971-2016 clay stabilizer performance evaluation method for oil and gas field fracturing acidification and water injection and Q/SH 0053-2010 clay stabilizer technical requirement. The clay stabilizers of example 5 and example 6 were measured for their anti-swelling rate and water washing resistance in water. The results are shown in Table 3.
TABLE 3 anti-swelling and Water washing resistance of Clay stabilizers
Figure GDA0002763308010000122
Figure GDA0002763308010000131
As can be seen from the table, the clay stabilizer of the invention has the anti-swelling rate higher than 85% and the water washing resistance rate higher than 90% in the clear water fracturing fluid under the addition of 0.2%; under the addition of 0.5 percent of clay stabilizer, the anti-swelling rate in the clear water fracturing fluid is higher than 90 percent, and the water washing resistance rate is higher than 90 percent; the clay stabilizers (potassium chloride and ammonium chloride) of the control inorganic salts showed less than 70% anti-swelling at 2.0% addition.
(2) Compatibility test
The clay stabilizers of examples 1 and 2 were observed for compatibility with the base fluid and acid fluid of the fracturing fluid, and the results are shown in table 2.
TABLE 4 compatibility test of Clay stabilizers
Figure GDA0002763308010000132
As can be seen from Table 4, the clay stabilizer of the present invention has no delamination, sedimentation and suspension phenomena when mixed with a fracturing fluid base and an acid solution, and has good compatibility.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.

Claims (4)

1. The preparation method of the star-shaped multi-cation surfactant is characterized in that the structural formula of the star-shaped multi-cation surfactant is as follows:
Figure FDA0002763307000000011
wherein R is1-is a long aliphatic chain with 12-18 carbon atoms in the carbon chain; r2-is-H or
Figure FDA0002763307000000012
The preparation method of the star-shaped polycation surfactant comprises the following steps:
adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into a long-chain fatty primary amine ethanol solution and an acid catalyst to perform aziridine ring-opening reaction, and reacting at 50-80 ℃ for 6-8 h;
under the alkalescent condition, adding methyl chloride or benzyl chloride reaction liquid into the reactant to carry out quaternization reaction, and reacting for 10-16 h at 50-70 ℃ under the protection of nitrogen; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
2. The method for preparing the star-shaped polycation-based surfactant according to claim 1, wherein the molar ratio of trimethylolpropane-tris (3-aziridinyl propionate) to the long-chain aliphatic primary amine in the aziridine ring-opening reaction is 1: 3.
3. The method for preparing the star multi-cation based surfactant according to claim 1, wherein the method comprises the following steps: in the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.
4. The method for preparing the star-shaped polycation-based surfactant according to claim 1, wherein the pH value is 9-10 under weak alkaline condition in the quaternization reaction, and the reaction solution is K2CO3And adjusting to alkalescence.
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WO2017132306A1 (en) * 2016-01-26 2017-08-03 Rhodia Operations Clay stabilizing agents and methods of use

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