CN112694412B - Betaine and preparation method and application thereof - Google Patents
Betaine and preparation method and application thereof Download PDFInfo
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- CN112694412B CN112694412B CN201911004129.9A CN201911004129A CN112694412B CN 112694412 B CN112694412 B CN 112694412B CN 201911004129 A CN201911004129 A CN 201911004129A CN 112694412 B CN112694412 B CN 112694412B
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Abstract
The invention relates to betaine and a preparation method and application thereof, and mainly solves the problems that under an acidic condition, the pH is reduced, a plurality of foaming agents fail and foam cannot be generated. By using betaine, the molecular formula is shown in the specification, wherein R is C 8 ～C 40 Aliphatic or aromatic hydrocarbon radicals; m+n is any number from 0 to 30; r is R 1 Is C 1 ～C 4 Alkylene or substituted alkylene of (a); p is an integer from 1 to 6; r is R 3 Is C 1 ～C 5 One or two or more of alkylene or substituted alkylene; r is R 2 H, C of a shape of 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 is R 4 Selected as H, C 1 ～C 5 Alkyl or substituted alkyl of (a),‑(C 3 H 6 O) x2 H、‑(C 2 H 4 O) y2 H, etc., solves the problem well, and can be used for generating foam under acidic conditions.
Description
Technical Field
The invention relates to betaine and a preparation method and application thereof.
Background
With the exploitation of oil and gas fields, the water content of the oil and gas fields is gradually increased, and geological conditions are more and more severe. There are increasing wells containing acid gases, such as hydrogen sulfide, carbon dioxide, which plug water, produce gas, and have difficulty in producing oil. How to improve the oil and gas exploitation rate and develop the residual reserve to the maximum extent has become an important task of the petroleum industry.
Gas flooding or gas lifting is one of the most effective methods for improving recovery efficiency of complex oil and gas reservoirs, especially difficult-to-recover reservoirs. However, in the gas displacement process, there is a serious technical problem that the viscosity contrast of underground crude oil and injected gas is large, so that the unfavorable fluidity ratio is caused, the early gas breakthrough is caused, and the sweep coefficient of an oil layer is reduced; and due to the heterogeneity of the reservoir, severe gas channeling can occur, especially when cracks or large tunnels exist, resulting in reduced oil production.
In order to increase the ability to seal off the high permeation layer, a number of studies have found that foam can enter and reduce the permeability of the high permeation layer. By adding the foam agent and mixing the gas, and performing displacement in the form of foam fluid, the high-permeability zone can be selectively blocked, the imbibition profile can be adjusted, and the sweep coefficient can be increased. The biggest difficulty encountered during gas-driven foam plugging applications is the difficulty in forming stable foam over long periods of time, especially in the presence of large amounts of acid gases or under acidic conditions.
Currently, there are three main categories of foaming agents on the market: anionic, nonionic and betaine foam. At present, most of foaming agents for enhanced oil recovery adopt a multi-component compound system, and simultaneously comprise nonionic surfactant and ionic surfactant, and assistants 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 uses sodium dodecyl benzene sulfonate as a foaming agent, and the foaming agent consists of modified guanidine gum, hydroxyethyl cellulose and dodecanol. Many surfactants are less active under pH influence in acidic conditions, and therefore many of these surfactants are used in alkali-containing systems, such as the patent CN1093589C discloses a foam complex flooding method in which the foam composition is composed of 0.5% -1.5% alkali, 0.05% -0.5% surfactant and 0.05% -0.5% polymer.
For this reason, the present invention developed a novel betaine that has an extremely strong ability to form foam under acidic conditions.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of reduced foam generation under acidic conditions, and provide a novel betaine. The betaine is clear and transparent under pH of 3, mineralization degree of 0-300000mg/L, and calcium and magnesium ion concentration of 0-10000mg/L, and supercritical acid gas CO at 100deg.C 2 Foam is formed under the regulation, and the half life reaches 1 h.
The second technical problem to be solved by the invention is to provide a preparation method of betaine corresponding to the technical problem.
The third technical problem to be solved by the invention is to provide 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 technical problems, the invention adopts the following technical scheme: a betaine of the general molecular formula:
wherein R is C 8 ～C 40 Aliphatic or aromatic hydrocarbon radicals; m+n is any number from 0 to 30; k is 0 or 1; r is R 1 Is C 1 ～C 4 Alkylene or substituted alkylene of (a); p is any one integer from 1 to 6; r is R 3 Is C 1 ～C 5 One or two or more of alkylene or substituted alkylene; r is R 2 Is H or C 1 ～C 5 Or (C) 3 H 6 O) 1-5 H, or (C) 2 H 4 O) 1-5 H, or R 3 N(R 4 )R 5 Or R is 3 N(R 4 )(R 5 )R 6 One or more than two of Y; r is R 4 Selected as H, C 1 ～C 5 Alkyl or substituted alkyl, - (C) 3 H 6 O) x2 H、-(C 2 H 4 O) y2 Any one of H, R 5 Selected as H, C 1 ～C 5 Alkyl or substituted alkyl, - (C) 3 H 6 O) x3 H、-(C 2 H 4 O) y3 Any one of H; r is R 7 Is 0 or R 8 One or more than two of Y and R 6 、R 8 Independently selected from C 1 ～C 5 Alkylene or substituted alkylene of (a); x1+x2+x3=0 to 15 and greater than 0; y1+y2+y3=0 to 15 and greater than 0; y is an anionic group that renders the formula electrically neutral.
In the above technical scheme, R is preferably C 8 ～C 30 Further preferably C 8 ～C 24 More preferably C 8 ～C 24 Alkyl or alkenyl of (a).
In the above-mentioned embodiments, the preferable range of m+n is any one of 0 to 20, and more preferably any one of 1 to 10.
In the technical scheme, R 1 ，R 3 Is independently selected from C 1 ～C 3 One or two or more of alkylene or substituted alkylene.
In the technical scheme, R 2 Is C 1 ～C 3 Alkyl or substituted alkyl, - (C) 3 H 6 O) x1 H、-(C 2 H 4 O) y1 One or more than two of H; r is R 4 Selected as C 1 ～C 3 Alkyl or substituted alkyl, - (C) 3 H 6 O) x2 H、-(C 2 H 4 O) y2 Any one of H, R 5 Selected as C 1 ～C 3 Alkyl or substituted alkyl, - (C) 3 H 6 O) x3 H、-(C 2 H 4 O) y3 Any one of H; x1+x2+x3=0 to 9 and greater than 0, more preferably x1+x2+x3=1 to 9; y1+y2+y3=0 to 9 and greater than 0, more preferably y1+y2+y3=1 to 9.
In the technical scheme, R 6 、R 8 Independently preferably selected from C 1 ～C 3 Alkylene of (C), more preferably R 6 、R 8 Is selected from C 1 ～C 3 An alkylene group of (a); y is preferably-HPO 4 — 、-COO — or-SO 3 -either, p is preferably 1 or 2 or 3.
In the above embodiments, the substituent in the substituted alkyl group or substituted alkylene group may be various substituents commonly used in the art, for example, but not limited to, a halogen substituent or a hydroxy substituent, preferably a hydroxy substituent.
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: a method for preparing betaine, comprising the steps of:
a) Haloalkyl polyether RO (C) 3 H 6 O) m (C 2 H 4 O) n R 1 Synthesis of Cl:
alkyl polyether RO (C) 3 H 6 O) m (C 2 H 4 O) n R 1 Carrying out halogenated dehydroxylation reaction on OH and thionyl chloride, and treating after the reaction is finished to obtain RO (C) 3 H 6 O) m (C 2 H 4 O) n R 1 Cl；
b) Alkyl polyethersTertiary amines
Is synthesized by the following steps:
the halogenated alkyl polyether RO (C) synthesized in a) is subjected to reaction 3 H 6 O) m (C 2 H 4 O) n R 1 Cl and secondary amine
Alkylation reaction is carried out, and tertiary amine +_ is obtained after the reaction is finished and the treatment is carried out>
Wherein R 'is' 2 H, C of a shape of H, C 1 ～C 5 Alkyl, -R 3 N(R 4 )R 5 、-R 3 N(R 4 )(R 5 )R 6 One or more than two of Y; r's' 4 And R'. 5 Independently selected as H or C 1 ～C 5 K=1;
c) Betaine (betaine)
Is synthesized by the following steps:
to be synthesized tertiary amine
And XR (X-ray) 6 Y is subjected to quaternization to give the betaine +.>
Where k=1.
In the technical scheme, in the halogenation reaction of the a), the molar ratio of the alkyl polyether to the thionyl chloride is preferably 1 (1-3), the reaction temperature is preferably 50-120 ℃, and the reaction time is 6-12 hours.
In the above technical scheme, in the alkylation reaction of 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 is 2 Selected from- (C) 3 H 6 O) x1 H or- (C) 2 H 4 O) y1 Any of H, and/or R 4 Selected from- (C) 3 H 6 O) x2 H or- (C) 2 H 4 O) y2 Any of H, and/or R 5 Selected from- (C) 3 H 6 O) x3 H or- (C) 2 H 4 O) y3 In any of H, R' 2 Is H, and/or R' 4 Is H, and/or R' 5 If H, step b) further comprises the steps of:
synthesizing the above
Alkoxylation with ethylene oxide and/or propylene oxide; after the reaction is finished, the +.>
In the above technical scheme, the tertiary amine and XR in the quaternization reaction in the step c) 6 The molar ratio of Y 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, comprising the steps of:
1) Alkyl tertiary amine
Is synthesized by the following steps:
halogenated alkane RR 1 Cl and secondary amine
Alkylation reaction is carried out, and tertiary amine +_ is obtained after the reaction is finished and the treatment is carried out>
Wherein R 'is' 2 H, C of a shape of H, C 1 ～C 5 Alkyl or R of (2) 3 N(R 4 )R 5 Or R is 3 N(R 4 )(R 5 )R 6 One or more than two of Y; r's' 4 And R'. 5 Independently selected as H or C 1 ～C 5 Alkyl of (a);
2) Betaine (betaine)
Is synthesized by the following steps:
the tertiary amine synthesized in 1) is reacted with
And XR (X-ray) 6 Y is subjected to quaternization to give the betaine +.>
In the above technical scheme, in the alkylation reaction in the 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 solution, in the step 1), when R 2 Selected from- (C) 3 H 6 O) x1 H or- (C) 2 H 4 O) y1 Any of H, and/or R 4 Selected from- (C) 3 H 6 O) x2 H or- (C) 2 H 4 O) y2 Any of H, and/or R 5 Selected from- (C) 3 H 6 O) x3 H or- (C) 2 H 4 O) y3 In any of H, R' 2 Is H, and/or R' 4 Is H, and/or R' 5 If H, the step 1) further comprises the following steps:
synthesizing the above
Carrying out an alkoxylation reaction; after the reaction is finished, the +.>
In the above technical scheme, the step 2) quaternization reactionIn this regard, tertiary amines with XR 6 The molar ratio of Y is preferably 1 (1-7), the reaction temperature is preferably 60-90 ℃, the reaction time is preferably 4-10 hours, and X is halogen.
In order to solve the fourth technical problem, the invention adopts the following technical scheme: the use of betaine as a foaming agent according to any one of the above technical solutions.
In the above technical scheme, the application is not particularly limited, and a person skilled in the art can utilize the betaine according to the foam agent oil displacement process, and the betaine can be applied to water shutoff and gas flooding enhanced oil recovery of an acid gas well, wherein the betaine dosage range is preferably 0.1% -1.0%, and more preferably 0.3% -0.6% in terms of weight percentage.
In the above technical scheme, for example, the betaine of the invention can be clarified and transparent under the condition of formation water with pH of 3, mineralization degree of 0-300000mg/L and calcium-magnesium ion concentration of 0-10000mg/L, and supercritical acid gas CO at 100 DEG C 2 Foam is formed under the regulation, the half-life period reaches 1h, and the foam is mixed with acidic CO in a porous medium 2 The gas resistance factor reaches 200.
The invention is characterized in that
And
can be characterized by infrared analysis spectrum, and the scanning range is 4000-400 cm -1 . The wave number 1464cm in FIG. 1 -1 The absorption peak of tertiary amine C-N, FIG. 1 wave number 1040cm -1 And FIG. 2 wave number 1073cm -1 The absorption peak is C-O-C bond, and the wave number is 2850-3000 cm in FIG. 1 and FIG. 2 -1 The characteristic peak of long-chain alkyl is shown in FIG. 2, wave number is 1594cm -1 The characteristic peak of the carboxylic acid group is shown, and the characteristic peak of the tertiary amine disappears.
The betaine can be applied to water shutoff and gas flooding enhanced oil recovery of an acid gas well, and the dosage range of the betaine is 0.1-1.0% by weight percent, and the preferable range is 0.3-0.6% by weight percent.
In the invention, the betaine designs polyamine and nonionic fragments in a molecular structure of a surfactant at the same time, so that a novel betaine is formed. 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 condition of formation water with pH of 3, mineralization degree of 0-300000mg/L and calcium-magnesium ion concentration of 0-10000mg/L, and supercritical acid gas CO is treated at 100 DEG C 2 Foam is formed under the regulation, the half-life period reaches 1h, and the foam is mixed with acidic CO in a porous medium 2 The gas resistance factor reaches 200, and a better technical effect is achieved.
Drawings
FIG. 1 is a chart C characterized by using an American Nicolet-5700 infrared spectrometer 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )C 3 H 6 N(CH 3 ) 2 Infrared spectrum of (scanning range 4000-650 cm) -1 )。
FIG. 2 is a synthetic product C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 Infrared spectrum of COO (scanning range 4000-650 cm) -1 )。
The wave number 1464cm in FIG. 1 -1 The absorption peak of tertiary amine C-N, FIG. 1 wave number 1040cm -1 And FIG. 2 wave number 1073cm -1 The absorption peak is C-O-C bond, and the wave number is 2850-3000 cm in FIG. 1 and FIG. 2 -1 The characteristic peak of long-chain alkyl is shown in FIG. 2, wave number is 1594cm -1 The characteristic peak of the carboxylic acid group is located, and the characteristic peak of the 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 ]
C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 Synthesis of COO
a)C 16 H 33 (C 2 H 4 O)C 2 H 4 Synthesis of Cl:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer, and gas absorbing unit 16 H 33 O(C 2 H 4 O) 2 330 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, the excess thionyl chloride is distilled off under reduced pressure to obtain C 16 H 33 O(C 2 H 4 O)C 2 H 4 Cl yield was 89%.
b)C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )C 3 H 6 N(CH 3 ) 2 Is synthesized by the following steps:
c synthesized in a) 16 H 33 O(C 2 H 4 O)C 2 H 4 174 g (0.5 mol) of Cl is added into a four-neck flask with a reflux condensing device, a thermometer and a stirrer, the temperature is heated to 70 ℃, 70 g of toluene is added, after the mixture is stirred uniformly, a mixed solution composed of 22 g (0.5 mol) of trimethyl-1, 3-propanediamine and 48 g (0.7 mol) of pyridine is slowly added dropwise, the temperature is controlled to be less than 60 ℃, and the temperature is raised to 85 ℃ after the dropwise addition for 2 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain trimethyl-1, 3-propanediamine to obtain the target intermediate C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )C 3 H 6 N(CH 3 ) 2 The yield thereof was found to be 85%.
c)C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 Synthesis of COO:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )C 3 H 6 N(CH 3 ) 2 128 g (0.3 mol), 100 g of isopropanol, heating to 60℃with stirring, and slowly adding 260 g (0.4 mol) of 20% sodium chloropropionate by a dropping funnel, and reacting at 90℃for 10 hours after the completion of the addition. After the reaction is finished, the sample is treated and then analyzed by High Performance Liquid Chromatography (HPLC), and C in the product 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 The COO content was 93wt%.
For C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )C 3 H 6 N(CH 3 ) 2 And C 16 H 33 O(C 2 H 4 O)C 2 H 4 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 COO was analyzed by using an infrared spectrometer of Nicolet-5700 in the U.S., and had characteristic peaks shown in FIG. 1 and FIG. 2, respectively.
[ example 2 ]
C 12 H 25 O(C 3 H 6 O)C 3 H 6 N(C 2 H 5 O)C 2 H 4 N(C 2 H 5 O) 2 CH 2 CH(OH)CH 2 SO 3 Is synthesized by (a)
a)C 12 H 25 O(C 3 H 6 O)C 3 H 6 Synthesis of Cl:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer, and gas absorbing unit 12 H 25 O(C 3 H 6 O) 2 H302 g (1.0 mol) and thionyl chloride 238 g (2.0 mol) and 5 g DMF were reacted at 100℃for 5 hours. After the reaction is finished, the excess thionyl chloride is distilled off under reduced pressure to obtain C 12 H 25 O(C 3 H 6 O)C 3 H 6 Cl yield was 91%.
b)C 12 H 25 O(C 3 H 6 O)C 3 H 6 N(C 2 H 5 O)C 2 H 4 N(C 2 H 5 O) 2 Is synthesized by the following steps:
c synthesized in a) 12 H 25 O(C 3 H 6 O)C 3 H 6 161 g (0.5 mol) of Cl was charged into a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, heated to 75℃and 70 g of toluene was added thereto, followed by stirring uniformly, and then H was slowly added dropwise with a dropping funnel 2 N-C 2 H 4 -NH 2 30 g (0.5 mol) and 48 g (0.7 mol) of pyridine, controlling the temperature to be less than 55 ℃, and raising the temperature to 85 ℃ after dripping for reaction for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product C 12 H 25 O(C 3 H 6 O)C 3 H 6 N(H)C 2 H 4 NH 2 The yield thereof was found to be 89%.
Adding C to a reactor equipped with a condensing unit, a stirring unit and a gas disperser 12 H 25 O(C 3 H 6 O)C 3 H 6 N(H)C 2 H 4 NH 2 140 g (0.4 mol), heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then purging 3-4 times with nitrogen 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 reaction; after the reaction is finished, purging the system with nitrogen to remove unreacted ethylene oxide, cooling, neutralizing, decoloring, filtering and dehydrating to obtain C 12 H 25 O(C 3 H 6 O)C 3 H 6 N(C 2 H 5 O)C 2 H 4 N(C 2 H 5 O) 2 The yield thereof was found to be 98%.
c)C 12 H 25 O(C 3 H 6 O)C 3 H 6 N(C 2 H 5 O)C 2 H 4 N(C 2 H 5 O) 2 CH 2 CH(OH)CH 2 SO 3 Is combined with (a)The method comprises the following steps:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer 12 H 25 O(C 3 H 6 O)C 3 H 6 N(C 2 H 5 O)C 2 H 4 N(C 2 H 5 O) 2 143 g (0.3 mol), 100 g of isopropanol, heating to 70℃with stirring, slowly dropping 300 g of 20% sodium 3-chloro-2-hydroxypropanesulfonate with a dropping funnel, and reacting at 90℃for 10 hours after the dropping was completed. After the reaction is finished, the sample is treated and then analyzed by High Performance Liquid Chromatography (HPLC), and C in the product 12 H 25 O(C 3 H 6 O)C 3 H 6 N(C 2 H 5 O)C 2 H 4 N(C 2 H 5 O) 2 CH 2 CH(OH)CH 2 SO 3 The content was 91% by weight.
[ example 3 ]
C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 N(C 3 H 7 O)(CH 3 )C 2 H 4 Synthesis of COO
a)C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 Synthesis of Cl:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer, and gas absorbing unit 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 4 H714 g (1.0 mol) and thionyl chloride 238 g (2.0 mol) and DMF 10 g were reacted at 80℃for 10 hours. After the reaction is finished, the excess thionyl chloride is distilled off under reduced pressure to obtain C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 Cl yield was 86%.
b)C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 N(C 3 H 6 O)(CH 3 ) Is synthesized by the following steps:
c synthesized in a) 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 365 g (0.5 mol) of Cl is added into a four-neck flask with a reflux condensing device, a thermometer and a stirrer, the temperature is heated to 77 ℃, 70 g of toluene is added, after the mixture is stirred uniformly, a mixture of 87 g (0.5 mol) of N, N' -trimethyldipropylene triamine and 48 g (0.7 mol) of pyridine is slowly dripped into the flask by a dripping funnel, the temperature is controlled to be less than 60 ℃, and the temperature is raised to 90 ℃ after the dripping is finished for reaction for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 NH(CH 3 ) The yield thereof was found to be 85%.
Adding C to a reactor equipped with a condensing unit, a stirring unit and a gas disperser 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 NH(CH 3 ) 361 g (0.4 mol), heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then purging 3-4 times with nitrogen to remove air in the system, adjusting the reaction temperature of the system to 130 ℃, slowly introducing 24 g of propylene oxide, and carrying out alkoxylation reaction; after the reaction is finished, purging the system with nitrogen to remove unreacted propylene oxide, cooling, neutralizing, decoloring, filtering and dehydrating to obtain C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 N(C 3 H 7 O)(CH 3 ) The yield thereof was found to be 92%.
c)C 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 N(C 3 H 7 O)(CH 3 )C 2 H 4 Synthesis of COO:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 N(C 3 H 7 O)(CH 3 ) 288 g (0.3 mol), 200 g of isopropanol, heating to 60℃with stirring, slowly dropping 175 g (0.3 mol) of 20% sodium chloroacetate with a dropping funnel, and reacting at 80℃for 10 hours after the completion of the dropping. After the reaction is finished, the sample is treated and then analyzed by High Performance Liquid Chromatography (HPLC), and C in the product 8 H 17 O(C 3 H 6 O) 7 (C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 2 N(C 3 H 7 O)(CH 3 )C 2 H 4 The COO content was 80wt%.
[ example 4 ]
a)C 24 H 49 O(C 2 H 4 O) 5 C 2 H 4 Synthesis of Cl:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer, and gas absorbing unit 24 H 49 O(C 2 H 4 O) 6 619 g (1.0 mol) of H and 357 g (3.0 mol) of thionyl chloride and 6 g of DMF were reacted at 90℃for 10 hours. After the reaction is finished, the excess thionyl chloride is distilled off under reduced pressure to obtain C 24 H 49 O(C 2 H 4 O) 5 C 2 H 4 Cl yield was 87%.
b)
Is synthesized by the following steps:
c synthesized in a) 24 H 49 O(C 2 H 4 O) 5 C 2 H 4 319 g (0.5 mol) of Cl was charged into a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, heated to 75℃and 70 g of toluene was added thereto, after stirring uniformly, a mixture of 94 g (0.5 mol) of tetramethyldipropylene triamine and 48 g (0.7 mol) of pyridine was slowly dropped into the flask via a dropping funnel, the temperature was controlled to be less than 60℃and the temperature was raised to 90℃after dropping, and reacted for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product
The yield thereof was found to be 82%.
c)
Is synthesized by the following steps:
adding into a four-neck round bottom flask equipped with a reflux condensing device, a thermometer and a stirrer
330 g (0.4 mol), 300 g of isopropanol, heating to 60℃with stirring, slowly dropping 300 g of 25% sodium chloroacetate with a dropping funnel, and reacting at 90℃for 10 hours after the completion of the dropping. After the reaction is finished, the sample is treated and then analyzed by High Performance Liquid Chromatography (HPLC), and the product is +.>
The content was 88wt%.
[ example 5 ]
C 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 N(C 2 H 4 OC 2 H 4 OC 2 H 4 OH)(CH 3 )C 2 H 4 SO 3 Is synthesized by (a)
a)C 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 Synthesis of Cl:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer, and gas absorbing unit 18 H 35 O(C 2 H 4 O) 4 H445 g (1.0 mol) and thionyl chloride 131 g (1.1 mol) and 4 g DMF were reacted at 90℃for 10 hours. After the reaction is finished, the excess thionyl chloride is distilled off under reduced pressure to obtain C 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 Cl yield was 87%.
b)C 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 N(C 2 H 4 O) 3 (CH 3 ) Is synthesized by the following steps:
c synthesized in a) 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 230 g (0.5 mol) of Cl is added into a four-neck flask with a reflux condensing device, a thermometer and a stirrer, the temperature is heated to 70 ℃, 70 g of toluene is added, after the mixture is stirred uniformly, a mixture of 122 g (0.5 mol) of N, N' -tetramethyl tripropylene tetramine and 48 g (0.7 mol) of pyridine is slowly dropped into the flask by a dropping funnel, the temperature is controlled to be less than 60 ℃, and the temperature is raised to 90 ℃ after the dropping is finished, and the reaction is carried out for 10 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain target C 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 NH(CH 3 ) The yield thereof was found to be 87%.
Adding C to a reactor equipped with a condensing unit, a stirring unit and a gas disperser 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 NH(CH 3 ) 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 reaction; after the reaction is finished, purging the system with nitrogen to remove unreacted ethylene oxide, cooling, neutralizing, decoloring, filtering and dehydrating to obtain C 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 N(C 2 H 4 OC 2 H 4 OC 2 H 4 OH)(CH 3 ) The yield thereof was found to be 90%. c) C (C) 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 N(C 2 H 4 OC 2 H 4 OC 2 H 4 OH)(CH 3 )C 2 H 4 SO 3 Is synthesized by the following steps:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 N(C 2 H 4 OC 2 H 4 OC 2 H 4 OH)(CH 3 ) 240 g (0.3 mol), 150 g of isopropanol, heating to 60℃with stirring, slowly dropping 500 g of 20% sodium chloropropanesulfonate with a dropping funnel, and reacting at 90℃for 10 hours after the dropping. After the reaction is finished, the sample is treated and then analyzed by High Performance Liquid Chromatography (HPLC), and C in the product 18 H 35 O(C 2 H 4 O) 3 C 2 H 4 (N(CH 3 )C 3 H 6 ) 3 N(C 2 H 4 OC 2 H 4 OC 2 H 4 OH)(CH 3 )C 2 H 4 SO 3 The content was 85wt%.
[ example 6 ]
C 18 H 37 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 Synthesis of COO
b)C 18 H 37 N(CH 3 )C 3 H 6 N(CH 3 ) 2 Is synthesized by the following steps:
c synthesized in a) 18 H 37 Cl 289 g (1.0 mol) was charged into a four-necked flask equipped with a reflux condenser, thermometer and stirrer, heated to 70℃and 70 g of toluene was added thereto, followed by stirring uniformly, and then a mixture of 22 g (0.5 mol) of trimethyl-1, 3-propanediamine and 48 g (0.7 mol) of pyridine was slowly dropped from a dropping funnel, the temperature was controlled to less than 60℃and the temperature was raised to 85℃after dropping, and reacted for 2 hours. Cooling, filtering, recrystallizing the crude product with ethanol, and vacuum drying to obtain the target intermediate product C 18 H 37 N(CH 3 )C 3 H 6 N(CH 3 ) 2 The yield thereof was found to be 90%.
c)C 18 H 37 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 Synthesis of COO:
c was added to a four neck round bottom flask equipped with reflux condensing unit, thermometer, stirrer 18 H 37 N(CH 3 )C 3 H 6 N(CH 3 ) 2 110 g (0.3 mol), 100 g of isopropanol, heating to 60℃with stirring, and slowly adding 260 g (0.4 mol) of 20% sodium chloropropionate by a dropping funnel, and reacting at 90℃for 10 hours after the completion of the addition. After the reaction is finished, the sample is treated and then analyzed by High Performance Liquid Chromatography (HPLC), and C in the product 18 H 37 N(CH 3 )(C 2 H 4 COO)C 3 H 6 N(CH 3 ) 2 C 2 H 4 The COO content was 91wt%.
[ example 7 ]
Taking the synthesized product [ examples 1-6 ], respectively preparing 0.5% aqueous solution in deionized water and simulated saline with mineralization degree of 300000mg/L and calcium ion of 10000mg/L, regulating pH to be 3, stirring for 10 minutes, and clarifying and transparentizing. The results of measuring the foaming amount and half-life at 100℃and 20MPa are shown in Table 1.
TABLE 1 foam foaming and half-life in deionized water and simulated brine
[ example 8 ]
Taking the synthesized product of examples 1-6, adjusting the pH to 3 in deionized water, stirring for 10 minutes to prepare 0.5% aqueous solution, wherein the gas is CO 2 Under the condition, plugging experiments are carried out in a porous medium, the temperature is 100 ℃, the back pressure is 20Mpa, the foam quality is 80%, and the formation resistance factors are shown in Table 2.
Taking the synthesized product [ examples 1-6 ], regulating pH to be 3 in simulated saline with the mineralization degree of 300000mg/L and the calcium ion of 10000mg/L, stirring for 10 minutes to prepare 0.5% aqueous solution, wherein the gas is CO 2 Under the condition, plugging experiments are carried out in a porous medium, the temperature is 100 ℃, the back pressure is 20Mpa, the foam quality is 80%, and the formation resistance factors are shown in Table 2.
TABLE 2 foam resistance factor formation in porous media
[ comparative example 1 ]
C 18 H 37 N(CH 3 ) 2 CH 2 COO and C 18 H 37 N(CH 3 ) 2 C 2 H 4 SO 3 The pH=3 was adjusted in deionized water and stirred for 10 minutes to prepare a 0.5% aqueous solution, the foaming amounts were 120 and 122mL, half lives were 29 and 25min, respectively, and the resistance factors of the porous media were 50 and 30, respectively, measured at 100℃and 20 MPa.
C 18 H 37 N(CH 3 ) 2 CH 2 COO and C 18 H 37 N(CH 3 ) 2 C 2 H 4 SO 3 Mixing with simulated saline with mineralization degree of 300000mg/L, calcium ion of 10000mg/L and pH=3 for 10 min to prepare 0.5% aqueous solution,the foaming amounts are 110 mL and 120mL respectively, the half lives are 30 min and 20min respectively, and the resistance factors of the porous medium are 45 and 50 respectively under the conditions of 100 ℃ and 20 MPa.
Claims (13)
1. A betaine of the general molecular formula:
wherein R is C 8 ～C 40 Is a fatty hydrocarbon group of (2); m+n is any number from 0 to 30; k is 1; r is R 1 Is C 1 ～C 4 An alkylene group of (a); p is an integer from 1 to 6; r is R 3 Is C 1 ～C 5 An alkylene group of (a); r is R 2 H, C of a shape of H, C 1 ～C 5 Alkyl, - (C) 3 H 6 O) x1 H、-(C 2 H 4 O) y1 H、-R 3 N(R 4 )R 5 or-R 3 N(R 4 )(R 5 )R 6 Any one of Y; r is R 4 Selected as H, C 1 ～C 5 Alkyl, - (C) 3 H 6 O) x2 H、-(C 2 H 4 O) y2 Any one of H, R 5 Selected as H, C 1 ～C 5 Alkyl, - (C) 3 H 6 O) x3 H、-(C 2 H 4 O) y3 Any one of H; r is R 7 Is R 8 Y，R 6 、R 8 Independently selected from C 1 ～C 5 An alkylene group of (a); x1+x2+x3=0 to 15 and greater than 0; y1+y2+y3=0 to 15 and greater than 0; y is an anionic group that renders the formula electrically neutral.
2. Betaine according to claim 1, characterized in that R is C 8 ～C 30 Is a fatty hydrocarbon group of (a).
3. Betaine according to claim 1, characterized in that R is C 8 ～C 24 Is a fatty hydrocarbon group of (a).
4. The betaine of claim 1, wherein m+n is any number from 0 to 20.
5. Betaine according to claim 1, characterized in that m+n is any number from 1 to 10.
6. Betaine according to claim 1, characterized in that R 1 ，R 3 Is C 1 ～C 3 An alkylene group of (a); r is R 2 Is C 1 ～C 3 Alkyl, - (C) 3 H 6 O) x1 H、-(C 2 H 4 O) y1 Any one of H; r is R 4 Selected as C 1 ～C 3 Alkyl, - (C) 3 H 6 O) x2 H、-(C 2 H 4 O) y2 Any one of H, R 5 Selected as C 1 ～C 3 Alkyl, - (C) 3 H 6 O) x3 H、-(C 2 H 4 O) y3 Any one of H; x1+x2+x3=0 to 9 and greater than 0; y1+y2+y3=0 to 9 and greater than 0; r is R 6 、R 8 Independently selected from C 1 ～C 3 An alkylene group of (a); the Y is-HPO 4 — 、-COO — or-SO 3 — Any one of the following.
7. Betaine according to claim 1, characterized in that said x1+x2+x3=1 to 9;
and/or y1+y2+y3=1 to 9;
and/or R 6 、R 8 Is selected from C 1 ～C 3 Alkylene groups of (a).
8. Betaine according to claim 1, characterized in that said p is 1 or 2 or 3.
9. A process for the preparation of betaine according to any one of claims 1 to 8, comprising the steps of:
a) Haloalkyl polyether RO (C) 3 H 6 O) m (C 2 H 4 O) n R 1 Synthesis of Cl:
alkyl polyether RO (C) 3 H 6 O) m (C 2 H 4 O) n R 1 Carrying out halogenated dehydroxylation reaction on OH and thionyl chloride, and treating after the reaction is finished to obtain RO (C) 3 H 6 O) m (C 2 H 4 O) n R 1 Cl；
b) Alkyl polyether tertiary amine
Is synthesized by the following steps:
the halogenated alkyl polyether RO (C) synthesized in a) is subjected to reaction 3 H 6 O) m (C 2 H 4 O) n R 1 Cl and secondary amine
Alkylation reaction is carried out, and tertiary amine is obtained after the reaction is finished and the tertiary amine is processed
Wherein R 'is' 2 H, C of a shape of H, C 1 ～C 5 Alkyl, -R 3 N(R 4 )R 5 or-R 3 N(R 4 )(R 5 )R 6 One or more than two of Y; r's' 4 And R'. 5 Independently selected as H or C 1 ～C 5 K=1;
c) Betaine (betaine)
Is synthesized by the following steps:
tertiary amine
And XR (X-ray) 6 Y is subjected to quaternization to give the betaine +.>
10. The preparation method according to claim 9, wherein in the halogenation reaction in the step a), the molar ratio of the alkyl polyether to the thionyl chloride is 1 (1-3), the reaction temperature is 50-120 ℃, and the reaction time is 6-12 hours; in the alkylation reaction of 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 step c), tertiary amine and XR 6 The 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.
11. A process for the preparation of betaine according to any one of claims 1 to 8, comprising the steps of:
1) Alkyl tertiary amine
Is synthesized by the following steps:
halogenated alkane RR 1 Cl and secondary amine
Alkylation reaction is carried out, and tertiary amine +_ is obtained after the reaction is finished and the treatment is carried out>
Wherein R 'is' 2 H, C of a shape of H, C 1 ～C 5 Alkyl or R of (2) 3 N(R 4 )R 5 Or R is 3 N(R 4 )(R 5 )R 6 One or more than two of Y; r's' 4 And R'. 5 Independently selected as H or C 1 ～C 5 Alkyl of (a);
2) Betaine (betaine)
Is synthesized by the following steps:
tertiary amine
And XR (X-ray) 6 Y is subjected to quaternization reaction to obtain the betaine
12. The preparation method according to claim 11, wherein in the alkylation reaction of 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 and XR 6 The 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.
13. Use of a betaine according to any of the claims 1 to 10 as a foaming agent.
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| JP2006143634A (en) * | 2004-11-18 | 2006-06-08 | Sanyo Chem Ind Ltd | Carboxybetaine |
| CN102276489A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Alkylphenol polyoxyethylene ether carboxylate type betaine and preparation method thereof |
| CN103422347A (en) * | 2013-07-31 | 2013-12-04 | 天津新纶科技有限公司 | Surface modifying agent used for chemical plating, surface modification treatment method and fabric chemical plating method |
| CN106140485A (en) * | 2016-08-03 | 2016-11-23 | 北京东信龙石油技术有限公司 | A kind of New Flotation Agent compositions |
| CN106590567A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Low tension foaming agent for high-salinity strata, and preparation method and applications thereof |
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2019
- 2019-10-22 CN CN201911004129.9A patent/CN112694412B/en active Active
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| JP2006143634A (en) * | 2004-11-18 | 2006-06-08 | Sanyo Chem Ind Ltd | Carboxybetaine |
| CN102276489A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Alkylphenol polyoxyethylene ether carboxylate type betaine and preparation method thereof |
| CN103422347A (en) * | 2013-07-31 | 2013-12-04 | 天津新纶科技有限公司 | Surface modifying agent used for chemical plating, surface modification treatment method and fabric chemical plating method |
| CN106590567A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Low tension foaming agent for high-salinity strata, and preparation method and applications thereof |
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