Betaine and preparation method and application thereof
阅读说明：本技术 甜菜碱及其制备方法和应用 (Betaine and preparation method and application thereof ) 是由 何秀娟 沈之芹 张卫东 李应成 于 2019-10-22 设计创作，主要内容包括：本发明涉及一种甜菜碱及其制备方法和应用,主要解决酸性条件下,pH降低,很多泡沫剂失效,无法生成泡沫的问题。通过采用甜菜碱,具有如下的分子通式,其中,R为C-8～C-(40)的脂肪烃基或芳烃基；m+n为0～30中的任意数；R-1为C-1～C-4的亚烷基或取代亚烷基；p为1-6的一个整数；R-3为C-1～C-5的亚烷基或取代亚烷基中的一种或两种以上；R-2为H、C-1～C-5的烷基或取代烷基、-(C-3H-6O)-(x1)H、-(C-2H-4O)-(y1)H等；R-4选为H、C-1～C-5的烷基或取代烷基、-(C-3H-6O)-(x2)H、-(C-2H-4O)-(y2)H等的技术方案,较好的解决了该问题,可用于酸性条件下生成泡沫。(The invention relates to betaine and a preparation method and application thereof, and mainly solves the problems that under an acidic condition, pH is reduced, a plurality of foaming agents fail to generate foams. By adopting betaine, the compound has the following molecular general formula, wherein R is C 8 ～C 40 Aliphatic hydrocarbon groups or aromatic hydrocarbon groups of (1); m + n is any number of 0-30; r 1 Is C 1 ～C 4 Alkylene or substituted alkylene of (a); p is an integer from 1 to 6; r 3 Is C 1 ～C 5 One or two or more of alkylene or substituted alkylene of (a); r 2 Is H, C 1 ～C 5 Alkyl or substituted alkyl, - (C) 3 H 6 O) x1 H、‑(C 2 H 4 O) y1 H, etc.; r 4 Is selected as H, C 1 ～C 5 Alkyl or substituted alkyl, - (C) 3 H 6 O) x2 H、‑(C 2 H 4 O) y2 H, etc., can be used for generating foams under acidic conditions.)
1. A betaine having the general molecular formula:
wherein R is C8～C40Aliphatic hydrocarbon groups or aromatic hydrocarbon groups of (1); m + n is any number of 0-30; k is 0 or 1; r1Is C1～C4Alkylene or substituted alkylene of (a); p is an integer from 1 to 6; r3Is C1～C5One or two or more of alkylene or substituted alkylene of (a); r2Is H, C1～C5Alkyl or substituted alkyl, - (C)3H6O)x1H、-(C2H4O)y1H、-R3N(R4)R5or-R3N(R4)(R5)R6One or more than two of Y; r4Is selected as H, C1～C5Alkyl or substituted alkyl, - (C)3H6O)x2H、-(C2H4O)y2Any one of HSeed, R5Is selected as H, C1～C5Alkyl group of (1), (C)3H6O)x3H、-(C2H4O)y3Any one of H; r7Is 0 or R8One or more of Y, R6、R8Is independently selected from C1～C5Alkylene or substituted alkylene of (a); x1+ x2+ x3 is 0-15 and greater than 0; y1+ y2+ y3 is 0-15 and greater than 0; y is an anionic group which renders the formula electrically neutral.
2. The betaine according to claim 1, wherein R is C8～C30Is more preferably C8～C24An aliphatic hydrocarbon group of (1).
3. The betaine according to claim 1, wherein m + n is any number from 0 to 20, more preferably any number from 1 to 10.
4. The betaine according to claim 1, wherein R is1，R3Is C1～C3One or two or more of alkylene or substituted alkylene of (a); r2Is C1～C3Alkyl or substituted alkyl, - (C)3H6O)x1H、-(C2H4O)y1One or more than two of H; r4Is selected as C1～C3Alkyl or substituted alkyl, - (C)3H6O)x2H、-(C2H4O)y2Any one of H, R5Is selected as C1～C3Alkyl or substituted alkyl, - (C)3H6O)x3H、-(C2H4O)y3Any one of H; x1+ x2+ x3 is 0 to 9 and greater than 0, more preferably x1+ x2+ x3 is 1 to 9; y1+ y2+ y3 is 0 to 9 and greater than 0, and more preferably y1+ y2+ y3 is 1 to 9; r6、R8Is independently selected from C1～C3More preferably R6、R8Is selected from C1～C3An alkylene group of (a); y is-HPO4 —、-COO—or-SO3 —Any one of them.
5. Betaine according to claim 1, characterized in that p is 1 or 2 or 3.
6. A method for preparing betaine according to any one of claims 1 to 5, comprising the steps of:
a) haloalkyl polyether RO (C)3H6O)m(C2H4O)n R1And (3) Cl synthesis:
alkyl polyether RO (C)3H6O)m(C2H4O)n R1OH and thionyl chloride are subjected to halogenation dehydroxylation reaction, and RO (C) is obtained after treatment after the reaction is finished3H6O)m(C2H4O)n R1Cl；
b) Alkyl polyether tertiary aminesThe synthesis of (2):
the halogenated alkyl polyether RO (C) synthesized in the step a)3H6O)m(C2H4O)nR1Cl and secondary amineAlkylation reaction is carried out, and tertiary amine is obtained after the reaction is finished and is treated
Wherein R'2Is H, C1～C5Alkyl of-R3N(R4)R5or-R3N(R4)(R5)R6One or more than two of Y; r'4And R'5Independently selected from H or C1～C5Alkyl of (a), k ═ 1;
c) betaineThe synthesis of (2):
reacting tertiary amineAnd XR6Quaternization of Y to obtain the betaine
7. The preparation method according to claim 6, wherein in the halogenation reaction in the step a), the alkyl polyether and the thionyl chloride are reacted for 6 to 12 hours at a molar ratio of 1 (1-3) and a reaction temperature of 50 to 120 ℃; in the alkylation reaction in the step b), the molar ratio of the halogenated alkyl polyether to the amine is 1 (1-2), the temperature is 70-150 ℃, and the reaction time is 6-12 hours; in the quaternization reaction of the step c), the tertiary amine is reacted with XR6The molar ratio of Y is 1 (1-7), the reaction temperature is 60-90 ℃, the reaction time is 4-10 hours, and X is halogen.
8. A method for preparing betaine according to any one of claims 1 to 5, comprising the steps of:
1) alkyl tertiary aminesThe synthesis of (2):
halogenated alkane RR1Cl and secondary amineAlkylation reaction is carried out, and tertiary amine is obtained after the reaction is finished and is treated
Wherein R'2Is H, C1～C5Alkyl or R3N(R4)R5Or R is3N(R4)(R5)R6One or more than two of Y; r'4And R'5Independently selected from H or C1～C5Alkyl groups of (a);
2) betaineThe synthesis of (2):
reacting tertiary amineAnd XR6Quaternization of Y to obtain the betaine
9. The preparation method according to claim 8, wherein in the alkylation reaction in the step 1), the molar ratio of the halogenated alkane to the amine is 1:1-2, the reaction temperature is 70-150 ℃, and the reaction time is 6-12 hours; in the quaternization reaction of the step 2), the tertiary amine is reacted with XR6The molar ratio of Y is 1 (1-7), the reaction temperature is 60-90 ℃, the reaction time is 4-10 hours, and X is halogen.
10. Use of a betaine according to any one of claims 1 to 7 as a foaming agent.
Technical Field
The invention relates to betaine and a preparation method and application thereof.
Background
Along with the exploitation of oil and gas fields, the water content of the oil and gas fields is gradually increased, and the geological conditions are more and more severe. There are more and more wells containing acid gases such as hydrogen sulfide and carbon dioxide, and these wells have difficulties in water shutoff, gas production and oil recovery. How to improve the oil and gas recovery rate and develop the residual reserves to the maximum extent becomes an important task in the petroleum industry.
Gas drive or gas lift is one of the most effective methods for enhancing the recovery efficiency of complex oil and gas reservoirs, especially of hard-to-recover oil reservoirs. However, in the gas displacement process, the method has a serious technical problem that the viscosity contrast of underground crude oil and injected gas is large, so that unfavorable fluidity ratio is caused, early gas breakthrough is caused, and the oil layer sweep coefficient is reduced; and because of the heterogeneity of the oil reservoir, especially when there are cracks or large tunnels, can produce the serious gas channeling, the oil recovery is reduced.
To improve the ability to seal high permeability layers, extensive research has shown that foam can enter and reduce the permeability of high permeability layers. By adding foaming agent and gas for mixing and displacing in the form of foam fluid, the high-permeability band can be selectively blocked, the liquid absorption section can be adjusted, and the sweep coefficient can be increased. The greatest difficulty encountered during gas drive foam plugging applications is the difficulty in forming a foam that is stable over time, particularly in the presence of large amounts of acidic gases or under acidic conditions.
There are three main categories of foaming agents currently on the market: anionic, nonionic and betaine foams. At present, the foaming agent for enhanced oil recovery mostly adopts a multi-component compound system, simultaneously contains a non-ionic surfactant and an ionic surfactant, and auxiliary agents such as alkali, alcohol, polymer and the like are added into part of the formula. For example, patent CN101619210A provides a carbon dioxide foam stabilizer for low permeability oil reservoirs, which selects sodium dodecyl benzene sulfonate as a foaming agent, and the foam stabilizer is composed of modified guar gum, hydroxyethyl cellulose, and dodecanol. Under acidic conditions, many surfactants are subject to pH-dependent activity reduction, and therefore many of these surfactants are used in alkali-containing systems, for example, patent CN1093589C discloses a foam complex flooding method, in which 0.5% -1.5% of alkali, 0.05% -0.5% of surfactant and 0.05% -0.5% of polymer are used to form a foam composition.
Therefore, the invention develops a new betaine which has extremely strong capability of generating foam under the acidic condition.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of reduced foam generation under acidic conditions, and a novel betaine is provided. The betaine is clear and transparent under the conditions of pH of 3, mineralization degree of 0-300000mg/L and calcium and magnesium ion concentration of 0-10000mg/L, and supercritical acidic gas CO is obtained at 100 deg.C2The foam is formed under regulation, and the half-life period reaches 1h。
The second technical problem to be solved by the present invention is to provide a method for preparing betaine corresponding to the technical problem.
The invention aims to solve the technical problem and provides another preparation method of betaine corresponding to the technical problem.
The fourth technical problem to be solved by the invention is to provide an application method of betaine corresponding to the technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a betaine having the general molecular formula:
wherein R is C8～C40Aliphatic hydrocarbon groups or aromatic hydrocarbon groups of (1); m + n is any number of 0-30; k is 0 or 1; r1Is C1～C4Alkylene or substituted alkylene of (a); p is any integer of 1-6; r3Is C1～C5One or two or more of alkylene or substituted alkylene of (a); r2Is H, or C1～C5Or substituted alkyl of (A), or (C)3H6O)1-5H, or (C)2H4O)1-5H, or R3N(R4)R5Or R is3N(R4)(R5)R6One or more than two of Y; r4Is selected as H, C1～C5Alkyl or substituted alkyl, - (C)3H6O)x2H、-(C2H4O)y2Any one of H, R5Is selected as H, C1～C5Alkyl or substituted alkyl, - (C)3H6O)x3H、-(C2H4O)y3Any one of H; r7Is 0 or R8One or more of Y, R6、R8Is independently selected from C1～C5Alkylene or substituted alkylene of (a); x1+ x2+ x3 is 0-15 and greater than 0; y1+ y2+ y3 is 0-15 and greater than 0; y is an anionic group which renders the formula electrically neutral.
In the above technical scheme, the preferable scheme of R is C8～C30Is more preferably C8～C24More preferably C8～C24Alkyl or alkenyl groups of (a).
In the above technical solutions, m + n is preferably any one number of 0 to 20, and more preferably any one number of 1 to 10.
In the above technical scheme, R1，R3Is independently selected from C1～C3One or two or more of alkylene or substituted alkylene groups of (a).
In the above technical scheme, R2Is C1～C3Alkyl or substituted alkyl, - (C)3H6O)x1H、-(C2H4O)y1One or more than two of H; r4Is selected as C1～C3Alkyl or substituted alkyl, - (C)3H6O)x2H、-(C2H4O)y2Any one of H, R5Is selected as C1～C3Alkyl or substituted alkyl, - (C)3H6O)x3H、-(C2H4O)y3Any one of H; x1+ x2+ x3 is 0 to 9 and greater than 0, more preferably x1+ x2+ x3 is 1 to 9; y1+ y2+ y3 is 0 to 9 and greater than 0, and more preferably y1+ y2+ y3 is 1 to 9.
In the above technical scheme, R6、R8Independently preferably from C1～C3More preferably R6、R8Is selected from C1～C3An alkylene group of (a); y is preferably-HPO4 —、-COO—or-SO3-p is preferably 1 or 2 or 3.
In the above technical scheme, the substituent in the substituted alkyl or substituted alkylene may be various substituents commonly used in the art, such as but not limited to a halogen substituent or a hydroxyl substituent, and preferably is a hydroxyl substituent.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing betaine comprises the following steps:
a) haloalkyl polyether RO (C)3H6O)m(C2H4O)n R1And (3) Cl synthesis:
alkyl polyether RO (C)3H6O)m(C2H4O)n R1OH and thionyl chloride are subjected to halogenation dehydroxylation reaction, and RO (C) is obtained after treatment after the reaction is finished3H6O)m(C2H4O)n R1Cl；
b) Alkyl polyether tertiary aminesThe synthesis of (2):
the halogenated alkyl polyether RO (C) synthesized in the step a)3H6O)m(C2H4O)nR1Cl and secondary amineAlkylation reaction is carried out, and tertiary amine is obtained after the reaction is finished and is treated
Wherein R'2Is H, C1～C5Alkyl of-R3N(R4)R5、-R3N(R4)(R5)R6One or more than two of Y; r'4And R'5Independently selected from H or C1～C5Alkyl of (a), k ═ 1;
c) betaineThe synthesis of (2):
synthesized tertiary amineAnd XR6Quaternization of Y to obtain the betaineWherein k is 1.
In the technical scheme, in the halogenation reaction of the step a), the alkyl polyether and the thionyl chloride are reacted for 6 to 12 hours at the molar ratio of 1 (1-3) and the reaction temperature of 50 to 120 ℃.
In the technical scheme, in the alkylation reaction in the step b), the molar ratio of the halogenated alkyl polyether to the amine is preferably 1 (1-2), the temperature is preferably 70-150 ℃, and the reaction time is preferably 6-12 hours; when R is2Is selected from- (C)3H6O)x1H or- (C)2H4O)y1Any of H, and/or R4Is selected from- (C)3H6O)x2H or- (C)2H4O)y2Any of H, and/or R5Is selected from- (C)3H6O)x3H or- (C)2H4O)y3R 'is any one of H'2Is H, and/or R'4Is H, and/or R'5If the value is H, the step b) further comprises the following steps:
synthesized by the aboveAlkoxylating with ethylene oxide and/or propylene oxide; after the reaction is finished, the product is obtained after treatment
In the above technical scheme, tertiary amine and XR in the quaternization reaction of step c)6The Y molar ratio is preferably 1 (1-7), the reaction temperature is preferably 60-90 ℃, the reaction time is preferably 4-10 hours, and the X is preferably halogen.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a method for preparing betaine comprises the following steps:
1) alkyl tertiary aminesThe synthesis of (2):
halogenated alkane RR1Cl and secondary amineAlkylation reaction is carried out, and tertiary amine is obtained after the reaction is finished and is treated
Wherein R'2Is H, C1～C5Alkyl or R3N(R4)R5Or R is3N(R4)(R5)R6One or more than two of Y; r'4And R'5Independently selected from H or C1～C5Alkyl groups of (a);
2) betaineThe synthesis of (2):
reacting the tertiary amine synthesized in 1)And XR6Quaternization of Y to obtain the betaine
In the above technical scheme, in the alkylation reaction in step 1), the molar ratio of the halogenated alkane to the amine is preferably 1 (1-2), the temperature is preferably 70-150 ℃, and the reaction time is preferably 6-12 hours.
In the above technical scheme, in the step 1), when R is2Is selected from- (C)3H6O)x1H or- (C)2H4O)y1Any of H, and/or R4Is selected from- (C)3H6O)x2H or- (C)2H4O)y2H in any ofAnd/or R5Is selected from- (C)3H6O)x3H or- (C)2H4O)y3R 'is any one of H'2Is H, and/or R'4Is H, and/or R'5If the value is H, the step 1) further comprises the following steps:
synthesized by the aboveCarrying out alkoxylation reaction; after the reaction is finished, the product is obtained after treatment
In the above technical scheme, in the quaternization reaction in the step 2), tertiary amine and XR (X-ray fluorescence)6The Y molar ratio is preferably 1 (1-7), the reaction temperature is preferably 60-90 ℃, the reaction time is preferably 4-10 hours, and the X is halogen.
In order to solve the fourth technical problem, the technical scheme adopted by the invention is as follows: use of betaine according to any of the above solutions to solve the problem as a foaming agent.
In the above technical solution, the application is not particularly limited, and those skilled in the art can utilize the betaine according to the foam flooding process, and the betaine of the present invention can be applied to water shutoff and gas flooding enhanced oil recovery of an acid gas well, and the betaine dosage range is preferably 0.1% to 1.0%, and more preferably 0.3% to 0.6% by weight.
In the technical scheme, for example, the betaine can be clarified and transparent under the conditions of pH 3, mineralization degree of 0-300000mg/L and concentration of calcium and magnesium ions of 0-10000mg/L, and supercritical acidic gas CO is generated at 100 DEG C2Forming foam under regulation, the half-life period reaches 1h, and reacting with acidic CO in a porous medium2The gas resistance factor reaches 200.
According to the inventionAndcan be characterized by infrared analysis spectrum, and the scanning range is 4000-400 cm-1. The wave number in FIG. 1 is 1464cm-1The absorption peak of tertiary amine C-N is shown in FIG. 1 with wave number of 1040cm-1And FIG. 2 wave number 1073cm-1The absorption peak is C-O-C bond, and the wave number in figure 1 and figure 2 is 2850-3000 cm-1Is a characteristic peak of long-chain alkyl, and the wave number of the graph is 1594cm-1The peak is a characteristic peak of the carboxylic acid group, and the characteristic peak of the tertiary amine disappears.
The betaine can be applied to water plugging and gas flooding enhanced oil recovery of an acid gas well, and the dosage range of the betaine is 0.1-1.0 percent by weight, and the preferred range is 0.3-0.6 percent by weight.
In the betaine, polyamine and a nonionic fragment are simultaneously designed in a surfactant molecular structure to form a novel betaine. The addition of polyamines enhances their ability to adapt to pH.
By adopting the technical scheme of the invention, the obtained betaine is clear and transparent under the conditions of pH 3, mineralization degree of 0-300000mg/L and concentration of calcium and magnesium ions of 0-10000mg/L in formation water, and supercritical acidic gas CO is generated at 100 DEG C2Forming foam under regulation, the half-life period reaches 1h, and reacting with acidic CO in a porous medium2The gas resistance factor reaches 200, and a better technical effect is achieved.
Drawings
FIG. 1 is C characterized by applying the American Nicolet-5700 infrared spectrometer16H33O(C2H4O)C2H4N(CH3)C3H6N(CH3)2Infrared spectrum (scanning range 4000- & ltwbr/& gt 650 cm)-1)。
FIG. 2 shows a synthetic product C16H33O(C2H4O)C2H4N(CH3)(C2H4COO)C3H6N(CH3)2C2H4Infrared spectrum of COO (scanning range 4000--1)。
The wave number in FIG. 1 is 1464cm-1The absorption peak of tertiary amine C-N is shown in FIG. 1 with wave number of 1040cm-1And FIG. 2 wave number 1073cm-1The absorption peak is C-O-C bond, and the wave number in figure 1 and figure 2 is 2850-3000 cm-1Is a characteristic peak of long-chain alkyl, and the wave number of the graph is 1594cm-1The characteristic peak of carboxylic acid group is shown, and the characteristic peak of tertiary amine disappears, thus proving the betaine product synthesized by the invention.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
C16H33O(C2H4O)C2H4N(CH3)(C2H4COO)C3H6N(CH3)2C2H4Synthesis of COO
a)C16H33(C2H4O)C2H4And (3) Cl synthesis:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer, a stirrer and a gas absorption device16H33O(C2H4O)2330 g (1.0 mol) of H, 149 g (1.25 mol) of thionyl chloride and 5 g of DMF are reacted at 90 ℃ for 10 hours. After the reaction is finished, excess thionyl chloride is evaporated under reduced pressure to obtain C16H33O(C2H4O)C2H4Cl, yield 89%.
b)C16H33O(C2H4O)C2H4N(CH3)C3H6N(CH3)2The synthesis of (2):
mixing C synthesized in a)16H33O(C2H4O)C2H4Adding 174 g (0.5 mol) of Cl into a four-neck flask with a reflux condenser, a thermometer and a stirrer, heating to 70 ℃, adding 70 g of toluene, stirring uniformly, slowly dropwise adding a mixed solution consisting of 22 g (0.5 mol) of trimethyl-1, 3-propane diamine and 48 g (0.7 mol) of pyridine, controlling the temperature to be less than 60 ℃, and heating to 85 ℃ after dropping for reaction for 2 hours. Cooling, passingFiltering, recrystallizing the crude product with ethanol, and vacuum drying to obtain trimethyl-1, 3-propane diamine to obtain target intermediate product C16H33O(C2H4O)C2H4N(CH3)C3H6N(CH3)2The yield thereof was found to be 85%.
c)C16H33O(C2H4O)C2H4N(CH3)(C2H4COO)C3H6N(CH3)2C2H4Synthesis of COO:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer and a stirrer16H33O(C2H4O)C2H4N(CH3)C3H6N(CH3)2128 g (0.3 mol) of isopropanol and 100 g of isopropanol are heated to 60 ℃ with stirring, 260 g (0.4 mol) of 20% sodium chloropropionate is slowly added dropwise via a dropping funnel, and after the addition is finished, the reaction is carried out for 10 hours at 90 ℃. After the reaction is finished, processing a sample, and analyzing by High Performance Liquid Chromatography (HPLC) to obtain C in the product16H33O(C2H4O)C2H4N(CH3)(C2H4COO)C3H6N(CH3)2C2H4The COO content was 93 wt%.
To C16H33O(C2H4O)C2H4N(CH3)C3H6N(CH3)2And C16H33O(C2H4O)C2H4N(CH3)(C2H4COO)C3H6N(CH3)2C2H4COO, using a U.S. Nicolet-5700 infrared spectrometer, having characteristic peaks shown in FIG. 1 and FIG. 2, respectively.
[ example 2 ]
C12H25O(C3H6O)C3H6N(C2H5O)C2H4N(C2H5O)2CH2CH(OH)CH2SO3Synthesis of (2)
a)C12H25O(C3H6O)C3H6And (3) Cl synthesis:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer, a stirrer and a gas absorption device12H25O(C3H6O)2H302 g (1.0 mol), thionyl chloride 238 g (2.0 mol) and DMF 5 g, at 100 ℃ for 5 hours. After the reaction is finished, excess thionyl chloride is evaporated under reduced pressure to obtain C12H25O(C3H6O)C3H6Cl, yield 91%.
b)C12H25O(C3H6O)C3H6N(C2H5O)C2H4N(C2H5O)2The synthesis of (2):
mixing C synthesized in a)12H25O(C3H6O)C3H6161 g (0.5 mol) of Cl was put into a four-neck flask equipped with a reflux condenser, a thermometer and a stirrer, heated to 75 ℃ and 70 g of toluene was added, and after stirring, H was slowly dropped into the flask via a dropping funnel2N-C2H4-NH230 g (0.5 mol) and 48 g (0.7 mol) of pyridine, controlling the temperature to be less than 55 ℃, and heating to 85 ℃ after dropping for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product C12H25O(C3H6O)C3H6N(H)C2H4NH2The yield thereof was found to be 89%.
Feeding C into a reactor equipped with a condensing device, a stirring device and a gas disperser12H25O(C3H6O)C3H6N(H)C2H4NH2140 g (0.4 mol), heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, and then purging with nitrogen for 3-4 times to removeRemoving air in the system, adjusting the reaction temperature of the system to 130 ℃, slowly introducing 53 g (1.2 mol) of ethylene oxide, and carrying out alkoxylation reaction; after the reaction is finished, purging the system by nitrogen to remove unreacted ethylene oxide, cooling, neutralizing, decoloring, filtering and dehydrating to obtain C12H25O(C3H6O)C3H6N(C2H5O)C2H4N(C2H5O)2The yield thereof was found to be 98%.
c)C12H25O(C3H6O)C3H6N(C2H5O)C2H4N(C2H5O)2CH2CH(OH)CH2SO3The synthesis of (2):
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer and a stirrer12H25O(C3H6O)C3H6N(C2H5O)C2H4N(C2H5O)2143 g (0.3 mol) of isopropanol and 100 g of isopropanol are heated to 70 ℃ with stirring, 300 g of 20% sodium 3-chloro-2-hydroxypropanesulfonate are slowly added dropwise via a dropping funnel, and after the dropwise addition is finished, the reaction is carried out for 10 hours at 90 ℃. After the reaction is finished, processing a sample, and analyzing by High Performance Liquid Chromatography (HPLC) to obtain C in the product12H25O(C3H6O)C3H6N(C2H5O)C2H4N(C2H5O)2CH2CH(OH)CH2SO3The content was 91 wt%.
[ example 3 ]
C8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2N(C3H7O)(CH3)C2H4Synthesis of COO
a)C8H17O(C3H6O)7(C2H4O)3C2H4And (3) Cl synthesis:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer, a stirrer and a gas absorption device8H17O(C3H6O)7(C2H4O)4H714 g (1.0 mol), thionyl chloride 238 g (2.0 mol) and DMF 10 g were reacted at 80 ℃ for 10 hours. After the reaction is finished, excess thionyl chloride is evaporated under reduced pressure to obtain C8H17O(C3H6O)7(C2H4O)3C2H4Cl, yield 86%.
b)C8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2N(C3H6O)(CH3) The synthesis of (2):
mixing C synthesized in a)8H17O(C3H6O)7(C2H4O)3C2H4Adding Cl 365 g (0.5 mol) into a four-neck flask with a reflux condenser, a thermometer and a stirrer, heating to 77 ℃, adding toluene 70 g, stirring uniformly, slowly dripping a mixed solution consisting of N, N' -trimethyl dipropylene triamine 87 g (0.5 mol) and pyridine 48 g (0.7 mol) into the flask by using a dropping funnel, controlling the temperature to be less than 60 ℃, and heating to 90 ℃ after dripping for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product C8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2NH(CH3) The yield thereof was found to be 85%.
Feeding C into a reactor equipped with a condensing device, a stirring device and a gas disperser8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2NH(CH3)361 g (0.4 mol), heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then purging for 3-4 times by using nitrogen to remove air in the system, then adjusting the reaction temperature of the system to 130 ℃, slowly introducing 24 g of propylene oxide, and carrying out alkoxylation; after the reaction is finished, purging the system by nitrogen to remove unreacted propylene oxide, cooling, neutralizing, decoloring, filtering and dehydrating to obtain C8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2N(C3H7O)(CH3) The yield thereof was found to be 92%.
c)C8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2N(C3H7O)(CH3)C2H4Synthesis of COO:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer and a stirrer8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2N(C3H7O)(CH3)288 g (0.3 mol) and 200 g of isopropanol were heated to 60 ℃ with stirring, and 175 g (0.3 mol) of 20% sodium chloroacetate was slowly added dropwise from a dropping funnel, and the reaction was carried out at 80 ℃ for 10 hours after completion of the addition. After the reaction is finished, processing a sample, and analyzing by High Performance Liquid Chromatography (HPLC) to obtain C in the product8H17O(C3H6O)7(C2H4O)3C2H4(N(CH3)C3H6)2N(C3H7O)(CH3)C2H4The COO content is 80 wt%.
[ example 4 ]
Synthesis of (2)
a)C24H49O(C2H4O)5C2H4And (3) Cl synthesis:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer, a stirrer and a gas absorption device24H49O(C2H4O)6619 g (1.0 mol) of H, 357 g (3.0 mol) of thionyl chloride and 6 g of DMF are reacted at 90 ℃ for 10 hours. After the reaction is finished, excess thionyl chloride is evaporated under reduced pressure to obtain C24H49O(C2H4O)5C2H4Cl, yield 87%.
b)The synthesis of (2):
mixing C synthesized in a)24H49O(C2H4O)5C2H4319 g (0.5 mol) of Cl is added into a four-neck flask with a reflux condenser, a thermometer and a stirrer, the mixture is heated to 75 ℃, 70 g of toluene is added, after uniform stirring, a mixed solution of 94 g (0.5 mol) of tetramethyl dipropylene triamine and 48 g (0.7 mol) of pyridine is slowly dripped into the flask by a dropping funnel, the temperature is controlled to be less than 60 ℃, and the temperature is raised to 90 ℃ after dripping for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate productThe yield thereof was found to be 82%.
c)The synthesis of (2):
adding into a four-neck round-bottom flask equipped with reflux condensing device, thermometer and stirrer330 g (0.4 mol)) 300 g of isopropanol is heated to 60 ℃ under stirring, 300 g of 25 percent sodium chloroacetate is slowly dripped by a dropping funnel, and the reaction is carried out for 10 hours at 90 ℃ after the dripping is finished. After the reaction is finished, processing a sample, analyzing by High Performance Liquid Chromatography (HPLC) to obtain the productThe content was 88 wt%.
[ example 5 ]
C18H35O(C2H4O)3C2H4(N(CH3)C3H6)3N(C2H4OC2H4OC2H4OH)(CH3)C2H4SO3Synthesis of (2)
a)C18H35O(C2H4O)3C2H4And (3) Cl synthesis:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer, a stirrer and a gas absorption device18H35O(C2H4O)4H445 g (1.0 mol) and thionyl chloride 131 g (1.1 mol) and 4 g DMF at 90 ℃ for 10 hours. After the reaction is finished, excess thionyl chloride is evaporated under reduced pressure to obtain C18H35O(C2H4O)3C2H4Cl, yield 87%.
b)C18H35O(C2H4O)3C2H4(N(CH3)C3H6)3N(C2H4O)3(CH3) The synthesis of (2):
mixing C synthesized in a)18H35O(C2H4O)3C2H4230 g (0.5 mol) of Cl is added into a four-neck flask with a reflux condenser, a thermometer and a stirrer, the mixture is heated to 70 ℃, 70 g of toluene is added, and after uniform stirring, 122 g (0.5 mol) of N, N' -tetramethyl tripropylene tetramine and pyridine 4 are slowly dripped into the mixture by a dropping funnel8 g (0.7 mol) of the mixture is put into a flask, the temperature is controlled to be less than 60 ℃, and the mixture is heated to 90 ℃ after dropping for 10 hours of reaction. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target C18H35O(C2H4O)3C2H4(N(CH3)C3H6)3NH(CH3) The yield thereof was found to be 87%.
Feeding C into a reactor equipped with a condensing device, a stirring device and a gas disperser18H35O(C2H4O)3C2H4(N(CH3)C3H6)3NH(CH3)268 g (0.4 mol), heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then purging with nitrogen for 3-4 times to remove air in the system, adjusting the reaction temperature of the system to 130 ℃, slowly introducing 53 g (1.2 mol) of ethylene oxide, and carrying out alkoxylation; after the reaction is finished, purging the system by nitrogen to remove unreacted ethylene oxide, cooling, neutralizing, decoloring, filtering and dehydrating to obtain C18H35O(C2H4O)3C2H4(N(CH3)C3H6)3N(C2H4OC2H4OC2H4OH)(CH3) The yield thereof was found to be 90%. c) C18H35O(C2H4O)3C2H4(N(CH3)C3H6)3N(C2H4OC2H4OC2H4OH)(CH3)C2H4SO3The synthesis of (2):
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer and a stirrer18H35O(C2H4O)3C2H4(N(CH3)C3H6)3N(C2H4OC2H4OC2H4OH)(CH3)240 g (0.3 mol) of isopropanol and 150 g of isopropanol were heated with stirringWhen the temperature is 60 ℃, 500 g of 20 percent sodium chloropropanesulfonate is slowly dripped by a dropping funnel, and the reaction is carried out for 10 hours at 90 ℃ after the dripping is finished. After the reaction is finished, processing a sample, and analyzing by High Performance Liquid Chromatography (HPLC) to obtain C in the product18H35O(C2H4O)3C2H4(N(CH3)C3H6)3N(C2H4OC2H4OC2H4OH)(CH3)C2H4SO3The content was 85 wt%.
[ example 6 ]
C18H37N(CH3)(C2H4COO)C3H6N(CH3)2C2H4Synthesis of COO
b)C18H37N(CH3)C3H6N(CH3)2The synthesis of (2):
mixing C synthesized in a)18H37Adding Cl 289 g (1.0 mol) into a four-neck flask with a reflux condenser, a thermometer and a stirrer, heating to 70 ℃, adding toluene 70 g, stirring uniformly, slowly dripping a mixed solution consisting of trimethyl-1, 3-propanediamine 22 g (0.5 mol) and pyridine 48 g (0.7 mol) by using a dropping funnel, controlling the temperature to be less than 60 ℃, and heating to 85 ℃ after dripping for reaction for 2 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product C18H37N(CH3)C3H6N(CH3)2The yield thereof was found to be 90%.
c)C18H37N(CH3)(C2H4COO)C3H6N(CH3)2C2H4Synthesis of COO:
adding C into a four-neck round-bottom flask provided with a reflux condensing device, a thermometer and a stirrer18H37N(CH3)C3H6N(CH3)2110 g (0.3 mol), 100 g of isopropanol, heating to 60 ℃ with stirring, slowly adding 20% of the mixture dropwise from a dropping funnel260 g (0.4 mol) of sodium chloropropionate was added dropwise and reacted at 90 ℃ for 10 hours. After the reaction is finished, processing a sample, and analyzing by High Performance Liquid Chromatography (HPLC) to obtain C in the product18H37N(CH3)(C2H4COO)C3H6N(CH3)2C2H4The COO content was 91 wt%.
[ example 7 ]
The synthesized products (examples 1-6) were mixed with deionized water and simulated saline with a degree of mineralization of 300000mg/L and a calcium ion concentration of 10000mg/L, respectively, and the pH was adjusted to 3, followed by stirring for 10 minutes to prepare 0.5% aqueous solutions, which were clear and transparent. The results of measuring the amount of foaming and half-life at 100 ℃ and 20MPa are shown in Table 1.
TABLE 1 foam rise and half-life in deionized and simulated saline
[ example 8 ]
The product synthesized in [ examples 1 to 6 ] was taken, adjusted to pH 3 in deionized water, stirred for 10 minutes to prepare a 0.5% aqueous solution with CO as the gas2Under the condition, a plugging experiment is carried out in a porous medium, the temperature is 100 ℃, the back pressure is 20Mpa, the foam quality is 80 percent, and the formed resistance factor is shown in a table 2.
Taking the product synthesized in [ examples 1-6 ], adjusting pH to 3 in simulated saline with degree of mineralization of 300000mg/L and calcium ion of 10000mg/L, stirring for 10 minutes to prepare 0.5% aqueous solution with CO gas as gas2Under the condition, a plugging experiment is carried out in a porous medium, the temperature is 100 ℃, the back pressure is 20Mpa, the foam quality is 80 percent, and the formed resistance factor is shown in a table 2.
TABLE 2 foam drag factor formation in porous media
[ COMPARATIVE EXAMPLE 1 ]
C18H37N(CH3)2CH2COO and C18H37N(CH3)2C2H4SO3The pH was adjusted to 3 in deionized water, stirred for 10 minutes to prepare a 0.5% aqueous solution, the amount of foam was 120 and 122mL, half-lives were 29 and 25min, respectively, and the drag factors of the porous medium were 50 and 30, respectively, measured at 100 ℃ and 20 MPa.
C18H37N(CH3)2CH2COO and C18H37N(CH3)2C2H4SO3The mixture was stirred in a simulated saline solution having a degree of mineralization of 300000mg/L, a calcium ion concentration of 10000mg/L and a pH of 3 for 10 minutes to prepare a 0.5% aqueous solution, and the foaming amounts were measured at 100 ℃ and 20MPa to be 110 and 120mL, respectively, half-lives thereof were 30 and 20min, respectively, and the drag factors of the porous medium were 45 and 50, respectively.
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