A temperature-resistant and high-salt-resistant high-surface-active polymerizable macromonomer and a preparation method thereof

Abstract

This invention discloses a heat-resistant, high-salt-resistant, highly surface-active polymerizable macromonomer and its preparation method. The structure of the heat-resistant, high-salt-resistant, highly surface-active polymerizable macromonomer is shown in Formula I, R 1 C2-C with a carbon-carbon double bond at the end 16 Hydrocarbon chain, R 2 It is an alkylene group, R 3 R 4 It is a C1-C3 alkyl group; R 5 The monomers are selected from tert-butyl, n-butyl, and benzyl; the number of C2H4O atoms p = 1 to 6. The method for preparing the temperature-resistant and high-salt-resistant polymerizable macromonomer of this invention uses widely available raw materials, is safe, simple, and easy to operate. Temperature can be precisely controlled, and the reaction is highly efficient. The high-surface-active, temperature-resistant, and high-salt-resistant polymerizable macromonomer prepared by this invention can self-polymerize and copolymerize with acrylamide. The resulting polymer oil displacement agent exhibits high surface activity and good salt resistance.

Description

Technical Field

[0001] This invention relates to a heat-resistant, high-salt-resistant, highly surface-active polymerizable macromonomer and its preparation method, belonging to the field of oil displacement agents. Background Technology

[0002] With my country's economic development, the consumption and demand for crude oil have been increasing year by year. Enhancing oil recovery is not only a trend in my country but also a global trend in oilfield development. Chemical flooding, as a crucial component of enhanced oil recovery technology, can generate significant social and economic benefits. Polymer flooding plays a vital role in chemical flooding. Polymers influence enhanced oil recovery by affecting sweep efficiency and displacement efficiency.

[0003] With the deepening exploitation of oil and gas resources, reservoir environments are becoming increasingly complex, placing higher demands on the performance of polymer flooding agents. Chemical agents successfully applied in ordinary reservoirs are prone to structural changes when applied to high-temperature, high-salinity reservoirs due to complex environmental factors. Because of the high salinity under these formation conditions, the molecular chains of commonly used partially hydrolyzed polyacrylamide flooding agents are prone to coiling and reacting with Ca... 2+ Mg 2+ Precipitation is easily generated, which affects the oil displacement effect of the oil displacement agent. Therefore, introducing temperature-resistant and salt-resistant functional groups into the oil displacement agent molecule is of great significance for improving the enhanced oil recovery effect of the oil displacement agent in complex reservoir environments.

[0004] Traditional batch reactors suffer from low mass and heat transfer efficiency, high liquid holdup, and uneven material concentration and temperature within the reactor. In contrast, continuous flow microreactors offer precise temperature control, high mass and heat transfer efficiency, experimental safety, and no scale-up effects. Therefore, this paper presents a method for synthesizing temperature-resistant, high-salt-resistant, polymerizable macromonomers via continuous flow preparation technology. This method enables the efficient synthesis of oil displacement agents and is of significant importance for improving oil recovery. Summary of the Invention

[0005] The purpose of this invention is to provide a method for synthesizing heat-resistant, salt-resistant, highly surface-active polymerizable macromonomers via continuous flow preparation technology. The method is highly efficient, produces few byproducts, is easy to operate, and the synthesized monomers can undergo self-polymerization or copolymerize with acrylamide to form highly surface-active, heat-resistant, and high-salt-resistant oil displacement agents.

[0006] The temperature-resistant, high-salt-resistant, highly surface-active polymerizable macromonomer provided by this invention has the structure shown in Formula I:

[0007]

[0008] In Equation I, R 1 C2-C with a carbon-carbon double bond at the end16 Hydrocarbon chain, preferably vinyl, R 2 It is an alkylene group, R 3 R 4 It is a C1-C3 alkyl group; R 5 It is selected from tert-butyl, n-butyl and benzyl; the number of C2H4O atoms p = 1 to 6, preferably 1 to 3.

[0009] The continuous flow preparation method for temperature-resistant, high-salt-resistant, polymerizable macromonomers provided by this invention employs a dilatation-M-type continuous flow microreactor, the structure of which is as follows:

[0010] Including the upper and lower substrates that fit together;

[0011] The lower substrate is provided with an M-shaped main channel, one end of which is connected to a confluence channel and an inlet channel in sequence, and the other end is connected to an outlet channel;

[0012] The upper substrate is provided with two inlets and one outlet, which are respectively connected to the inlet channel and the outlet channel;

[0013] Several hybrid expansion and contraction units are arranged on the M-shaped main channel. The hybrid expansion and contraction unit refers to the structure formed by the inward bulge of the pipe wall of the M-shaped main channel.

[0014] In the expanding / contracting M-type continuous flow microreactor, the lengths of several sections of the M-type main flow channel are equal, preferably 1800–2200 μm, and the widths are preferably 190–210 μm.

[0015] In the expanding / contracting M-type continuous flow microreactor, the corner of the M-type main channel is arc-shaped, and the angle of the arc is preferably 117-125°.

[0016] In the M-type continuous flow microreactor, the mixing and diffusion units are arranged periodically on the M-type main channel;

[0017] The two adjacent hybrid expansion and contraction units are arranged in opposite directions and staggered.

[0018] In the M-type continuous flow microreactor, 3 to 4 mixing and expanding units are provided on each channel of the M-type main channel.

[0019] In the M-type continuous flow microreactor, the mixing and expanding unit includes a water-facing surface, a water-following surface, and a circular arc boundary.

[0020] The water-facing surface and the water-following surface are both tangentially connected to the circular arc boundary.

[0021] In the expanding-contracting M-type continuous flow microreactor, the angle α between the water-facing surface and the extension line of the M-type main channel wall is greater than the angle β between the water-draining surface and the extension line of the M-type main channel wall.

[0022] The radius of the arc angle formed by the connection between the water-facing surface and the water-drifting surface is 38–42 μm, preferably 40 μm.

[0023] In the aforementioned expanding-contracting M-type continuous flow microreactor, the diameter reduction rate of the mixing expanding-contracting unit relative to the M-type main channel is 73-77%, preferably 75%. The "diameter reduction rate" refers to the reduction in the channel width and hydraulic diameter caused by the change in wall shape, and the ratio of the reduction amount to the original width of the main channel.

[0024] Specifically, the present invention employs four interconnected expanding-contraction M-type continuous flow microreactors, with the specific connection relationships as follows:

[0025] The four expanding-contraction M-type continuous flow microreactors are connected sequentially as a first-stage expanding-contraction M-type continuous flow microreactor, a second-stage expanding-contraction M-type continuous flow microreactor, a third-stage expanding-contraction M-type continuous flow microreactor, and a fourth-stage expanding-contraction M-type continuous flow microreactor, respectively, with the following connection relationships:

[0026] The outlet of the first-stage expanding-contraction M-type continuous flow microreactor is connected to one of the inlets of the second-stage expanding-contraction M-type continuous flow microreactor, the outlet of the second-stage expanding-contraction M-type continuous flow microreactor is connected to one of the inlets of the third-stage expanding-contraction M-type continuous flow microreactor, and the outlet of the third-stage expanding-contraction M-type continuous flow microreactor is connected to one of the inlets of the fourth-stage expanding-contraction M-type continuous flow microreactor.

[0027] The continuous flow preparation method for preparing temperature-resistant, high-salt-resistant, polymerizable macromonomers on the aforementioned expanded-contraction M-type continuous flow microreactor includes the following steps:

[0028] S1. The amine and aldehyde are introduced into the inlet channel of the first-stage expanding-contracting M-type continuous flow microreactor at flow rates q1 and q2, respectively, and the reaction temperature is controlled at T1.

[0029] S2. The product obtained in step 1 is introduced through one of the inlets of the two-stage expansion-contraction M-type continuous flow microreactor, while the carboxylic acid is introduced through the other inlet of the two-stage expansion-contraction M-type continuous flow microreactor at a flow rate of q3, and the reaction temperature is controlled at T2.

[0030] S3. The product obtained in step 2 is introduced through one inlet of the three-stage expansion-contraction M-type continuous flow microreactor, and at the same time, isonitrile is introduced through the other inlet of the three-stage expansion-contraction M-type continuous flow microreactor at a flow rate of q4, and the reaction temperature is controlled at T3.

[0031] S4. The product obtained in step 3 is introduced into one inlet of the four-stage expansion-contraction M-type continuous flow microreactor, and at the same time, an aqueous solution of sodium 2-haloethyl sulfonate is introduced into the other inlet of the four-stage expansion-contraction M-type continuous flow microreactor at a flow rate of q5, and the reaction temperature is controlled at T4.

[0032] S5. The product solution obtained from the outlet of the four-stage expansion-contraction M-type continuous flow microreactor is subjected to vacuum distillation to achieve continuous flow preparation of temperature-resistant, high-salt-resistant, polymerizable macromonomers.

[0033] In the above continuous flow preparation method, in step S1, the amine is N,N-dimethylethylenediamine, 1-(3-aminopropyl)pyrrolidine, or 4-amino-1-methylpiperidine, 3-diethylaminopropylamine;

[0034] The aldehyde is 4-(methoxytriethyleneoxy)carboxybenzaldehyde, which can be synthesized according to the method reported in the literature Angew. Chem. Int. Ed. 2008, 47, 8072-8074;

[0035] The flow rate q1 is 0.5–8 mL / min, the flow rate q2 is 0.5–8 mL / min, and the temperature T1 is 25–45 °C.

[0036] In the above continuous flow preparation method, in step S2, the carboxylic acid is C3-C 17 Alkenyl carboxylic acid, preferably acrylic acid;

[0037] The flow rate q3 is 0.1 to 1 mL / min, and the temperature T2 is 25 to 45 °C.

[0038] In the above continuous flow preparation method, in step S3, the isonitrile is tert-butylisocyanate, benzylisocyanate or n-butylisocyanate;

[0039] The flow rate q4 is 0.6–8 mL / min, and the temperature T3 is 25–45 °C.

[0040] In step S3, the sodium 2-haloethylsulfonate is sodium 2-chloroethylsulfonate or sodium 2-bromoethylsulfonate; the flow rate q5 is 1-8 mL / min; and the temperature T4 is 65-95 °C.

[0041] In the above continuous flow preparation method, the molar ratio of the amine, the aldehyde, the carboxylic acid, the isonitrile, and the sodium 2-haloethylsulfonate is 1:0.8-1.2:1:0.8-1.2:1-1.5;

[0042] Unless otherwise specified, the amines, aldehydes, carboxylic acids and isonitriles are introduced in pure form. 4-(methoxytriethyleneoxy)carboxybenzaldehyde in S1 is prepared as a solution in tetrahydrofuran with a concentration of 0.5–2.0 mol / L, specifically 1 mol / L.

[0043] The method for preparing the temperature-resistant and high-salt-resistant polymerizable macromonomer of this invention has a wide range of raw material sources, is safe and easy to operate, allows for precise temperature control, and results in a highly efficient reaction. The high surface activity, temperature-resistant and high-salt-resistant polymerizable macromonomer prepared by this invention can self-polymerize and copolymerize with acrylamide. The resulting polymer oil displacement agent has high surface activity and good salt resistance. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the overall structure of the expanding / contracting M-type continuous flow microreactor used in this invention.

[0045] Figure 2 This is a schematic diagram of the structure at the inlet of the flow channel of the expanding / contracting M-type continuous flow microreactor used in this invention.

[0046] Figure 3 This is an enlarged schematic diagram of the flow channel expansion unit structure of the M-type continuous flow microreactor used in this invention.

[0047] Figure 4 This is a schematic diagram of the reactor substrate of the expanding / contracting M-type continuous flow microreactor used in this invention.

[0048] The markings in the diagram are as follows:

[0049] 1 Upper substrate, 2 Lower substrate, 3 Inlet channel, 4 Confluence channel, 5 M-type main channel, 6 Outlet channel, 7 Mixing expansion and contraction unit, 8 Arc corner at the corner of the M-type main channel, 9 Water-facing surface, 10 Water-following surface, 11 Arc boundary at the connection between the water-facing and water-following surfaces of the mixing expansion and contraction unit, a Water phase inlet, b Oil phase inlet, c Outlet.

[0050] Figures 5-7 The images show the mixing effect cloud diagrams of the expanding-contraction M-type continuous flow microreactor used in this invention under three conditions: oil phase viscosity of 1 Pa·s and inlet velocity of 0.1 m / s, oil phase viscosity of 0.1 Pa·s and inlet velocity of 0.1 m / s, and oil phase viscosity of 0.1 Pa·s and inlet velocity of 0.5 m / s. Detailed Implementation

[0051] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0052] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0053] like Figure 1The diagram shown is a schematic representation of the overall structure of the expanding / contracting M-type continuous flow microreactor used in this invention, including an upper substrate 1 and a lower substrate 2 that fit together. Figure 3 As shown, the lower substrate 2 is provided with an M-shaped main channel 5. One end of the M-shaped main channel 5 is connected to the confluence channel 4 and the inlet channel 3 in sequence, and the other end is connected to the outlet channel 6. The upper substrate 1 is provided with a water phase inlet a, an oil phase inlet b, and an outlet c. The water phase inlet a and the oil phase inlet b are connected to the inlet channel 3, and the outlet c is connected to the outlet channel 6.

[0054] like Figure 3 As shown, the M-shaped main channel 5 is arranged in a serpentine pattern in the lower substrate 2. Several segments of the M-shaped main channel 5 have equal lengths, preferably 1800–2200 μm, and a width preferably 190–210 μm. The corners of the M-shaped main channel 5 are rounded (rounded corners 8 at the corners of the M-shaped main channel), and the angle of the rounded corners is preferably 117–125°. Several hybrid expansion and contraction units 7 are arranged on the M-shaped main channel 5. The hybrid expansion and contraction unit 7 refers to the structure formed by the inward bulge of the tube wall of the M-shaped main channel 5, such as… Figure 2 and Figure 3 As shown. The hybrid expansion and contraction units 7 are arranged periodically on the M-shaped main channel 5. Three hybrid expansion and contraction units 7 are set on each channel of the M-shaped main channel 5, and two adjacent hybrid expansion and contraction units 7 are arranged in opposite directions and staggered.

[0055] like Figure 3 As shown, the hybrid expansion and contraction unit 7 includes a water-facing surface 9, a water-following surface 10, and an arc boundary 11. The water-facing surface 9 and the water-following surface 10 are tangentially connected to the arc boundary 11. The angle α between the water-facing surface 9 and the extension line of the pipe wall of the M-shaped main channel 5 is greater than the angle β between the water-following surface 10 and the extension line of the pipe wall of the M-shaped main channel 5. Preferably, the radius of the arc angle formed by the connection of the water-facing surface 9 and the water-following surface 10 is 38-42 μm. In this embodiment, the angle α is 49°, the angle β is 32°, and the radius of the arc corner is 40 μm.

[0056] In this M-type continuous flow microreactor, the diameter reduction ratio of the mixing and expanding unit 7 relative to the main flow channel is 0.75.

[0057] In this expanding-contraction M-type continuous flow microreactor, the width of the inlet channel 3 is 200 μm, the width of the confluence channel 4 is 200 μm, the width of the M-type main channel 5 is 200 μm, the radius of the arc corner at the corner of the M-type main channel 5 is 200 μm, and the angle between two adjacent branch channels is 60°.

[0058] When using this M-type continuous flow microreactor, liquid water enters the reactor from the aqueous phase inlet a, and silicone oil, which is immiscible with water, enters the reactor from the oil phase inlet b. The velocity of both liquid phase inlets is 0.1 m / s. The liquids flow through each mixing and expansion unit 7 for thorough mixing and then flow out of the reactor from the outlet channel 6 and outlet c.

[0059] Specifically, from the simulation effect cloud map Figure 5 , Figure 6 , Figure 7 It can be seen that the density of silicone oil is 963 kg / m³. 3 The viscosity is 1 Pa·s or 0.1 Pa·s (the density of liquid water is 998.2 kg / m³). 3 When the viscosity is 0.001003 Pa·s and the inlet velocity is 0.1 m / s or 0.5 m / s, the straight-line distances from the starting point when the water phase accounts for 0.5 ± 0.01% of the volume (green represents 0.5% water phase) are 6.01 mm, 7.65 mm and 5.81 mm respectively.

[0060] When applying this M-type continuous flow microreactor, the inlet velocity is adjusted to adapt to different fluid mixing conditions and to ensure sufficient residence time; the diameter reduction ratio of the mixing and diffusion unit is appropriately adjusted to accommodate microparticles of different sizes.

[0061] High-purity functionalized acrylamide molecules were prepared using the aforementioned expanded-contraction M-type continuous flow microreactor, employing four interconnected expanded-contraction M-type continuous flow microreactors:

[0062] Four expanding-contraction M-type continuous flow microreactors are connected sequentially as a first-stage, second-stage, third-stage, and fourth-stage expanding-contraction M-type continuous flow microreactor, respectively, with the following connection relationships:

[0063] The outlet of the first-stage expanding-shrinkage M-type continuous flow microreactor is connected to one inlet of the second-stage expanding-shrinkage M-type continuous flow microreactor, the outlet of the second-stage expanding-shrinkage M-type continuous flow microreactor is connected to one inlet of the third-stage expanding-shrinkage M-type continuous flow microreactor, and the outlet of the third-stage expanding-shrinkage M-type continuous flow microreactor is connected to one inlet of the fourth-stage expanding-shrinkage M-type continuous flow microreactor.

[0064] The reaction volume of each expanding / contracting M-type continuous flow microreactor is 60 mL.

[0065] Example 1

[0066] 1. A tetrahydrofuran alcohol solution of 3-diethylaminopropylamine (concentration 1 mol / L) was injected into the first-stage M-type microfluidic reactor at a flow rate of 0.946 mL / min. A tetrahydrofuran solution of 4-(methoxytriethyleneoxy)carboxybenzaldehyde was injected into another inlet channel of the first-stage M-type microfluidic reactor at a flow rate of 6 mL / min. The heating module was controlled to maintain the reaction temperature at 30℃ and the retention time was 8.64 min.

[0067] 2. The reaction product synthesized in step 1 is fed into a secondary M-type microfluidic reactor. Acrylic acid is then injected into the secondary inlet of the second stage at a flow rate of 0.411 mL / min. The heating module is controlled to maintain the reaction at 30°C for a retention time of 8.16 min.

[0068] 3. The reaction product synthesized in step 2 is fed into a three-stage M-type microfluidic reactor. Then, n-butylisocyanate is injected into the third-stage sub-inlet at a flow rate of 0.628 mL / min. The heating module is controlled to keep the reaction at 30°C and the retention time is 7.51 min.

[0069] 4. The reaction product synthesized in step (3) is fed into a four-stage M-type microfluidic reactor. At the same time, an aqueous solution of sodium 2-chloroethylsulfonate is fed into the fourth-stage auxiliary inlet at a flow rate of 6 mL / min. The heating module is controlled to keep the reaction at 80°C and the retention time is 4.29 min.

[0070] 5. The product solution produced at the outlet of the four-stage M-type microfluidic reactor is subjected to vacuum distillation to remove tetrahydrofuran and water, and then purified with a mixture of acetone and water to obtain a white solid heat-resistant, high-salt-resistant polymerizable macromonomer.

[0071] Example 2

[0072] 1. A tetrahydrofuran alcohol solution of N,N-dimethylethylenediamine (concentration 1 mol / L) was injected into the first-stage M-type microfluidic reactor at a flow rate of 0.655 mL / min. A tetrahydrofuran solution of 4-(methoxytriethyleneoxy)carboxybenzaldehyde was injected into another inlet channel of the first-stage M-type microfluidic reactor at a flow rate of 6 mL / min. The heating module was controlled to maintain the reaction temperature at 30℃ and the retention time was 9.02 min.

[0073] 2. The reaction product synthesized in step 1 is fed into a secondary M-type microfluidic reactor. Then, acrylic acid is injected into the secondary inlet of the second stage at a flow rate of 0.411 mL / min. The heating module is controlled to maintain the reaction at 30°C for a retention time of 8.49 min.

[0074] 3. The reaction product synthesized in step 2 is fed into a three-stage M-type microfluidic reactor. Then, n-butylisocyanate is injected into the third-stage sub-inlet at a flow rate of 0.628 mL / min. The heating module is controlled to keep the reaction at 30°C and the retention time is 7.80 min.

[0075] 4. The reaction product synthesized in step 3 is fed into a four-stage M-type microfluidic reactor. At the same time, an aqueous solution of sodium 2-chloroethylsulfonate is fed into the fourth-stage auxiliary inlet at a flow rate of 6 mL / min. The heating module is controlled to maintain the reaction at 80°C for a retention time of 4.38 min.

[0076] 5. The product solution produced at the outlet of the four-stage M-type microfluidic reactor is subjected to vacuum distillation to remove tetrahydrofuran and water, and then purified with a mixture of acetone and water to obtain a white solid heat-resistant, high-salt-resistant polymerizable macromonomer.

[0077] Example 3

[0078] 1. 1-(3-aminopropyl)pyrrolidine was injected into the first-stage M-type microfluidic reactor at a flow rate of 0.759 mL / min, and a tetrahydrofuran solution of 4-(methoxytriethyleneoxy)carboxybenzaldehyde was injected into another inlet channel of the first-stage M-type microfluidic reactor at a flow rate of 6 mL / min. The heating module was controlled to maintain the reaction temperature at 30°C and the retention time was 8.88 min.

[0079] 2. The reaction product synthesized in step 1 is fed into a secondary M-type microfluidic reactor. Acrylic acid is then injected into the secondary inlet of the second stage at a flow rate of 0.411 mL / min. The heating module is controlled to maintain the reaction at 30°C for a retention time of 8.37 min.

[0080] 3. The reaction product synthesized in step 2 is fed into a three-stage M-type microfluidic reactor. Then, n-butylisocyanate is injected into the third-stage sub-inlet at a flow rate of 0.628 mL / min. The heating module is controlled to keep the reaction at 30°C and the retention time is 7.69 min.

[0081] 4. The reaction product synthesized in step 3 is fed into a four-stage M-type microfluidic reactor. At the same time, an aqueous solution of sodium 2-chloroethylsulfonate is fed into the fourth-stage auxiliary inlet at a flow rate of 6 mL / min. The heating module is controlled to maintain the reaction at 80°C for a retention time of 4.35 min.

[0082] 5. The product solution produced at the outlet of the four-stage M-type microfluidic reactor is subjected to vacuum distillation to remove tetrahydrofuran and water, and then purified with a mixture of acetone and water to obtain a white solid heat-resistant, high-salt-resistant polymerizable macromonomer.

[0083] Example 4

[0084] 1. 4-Amino-1-methylpiperidine was injected into the first-stage M-type microfluidic reactor at a flow rate of 0.753 mL / min. A tetrahydrofuran solution of 4-(methoxytriethyleneoxy)carboxybenzaldehyde was injected into another inlet channel of the first-stage M-type microfluidic reactor at a flow rate of 6 mL / min. The heating module was controlled to maintain the reaction temperature at 30°C and the retention time was 8.88 min.

[0085] 2. The reaction product synthesized in step 1 is fed into a secondary M-type microfluidic reactor. Acrylic acid is then injected into the secondary inlet of the second stage at a flow rate of 0.411 mL / min. The heating module is controlled to maintain the reaction at 30°C for a retention time of 8.38 min.

[0086] 3. The reaction product synthesized in step 2 is fed into a three-stage M-type microfluidic reactor. Then, n-butylisocyanate is injected into the third-stage sub-inlet at a flow rate of 0.628 mL / min. The heating module is controlled to keep the reaction at 30°C and the retention time is 7.70 min.

[0087] 4. The reaction product synthesized in step 3 is fed into a four-stage M-type microfluidic reactor. At the same time, an aqueous solution of sodium 2-chloroethylsulfonate is fed into the fourth-stage auxiliary inlet at a flow rate of 6 mL / min. The heating module is controlled to maintain the reaction at 80°C for a retention time of 4.35 min.

[0088] 5. The product solution produced at the outlet of the four-stage M-type microfluidic reactor is subjected to vacuum distillation to remove tetrahydrofuran and water, and then purified with a mixture of acetone and water to obtain a white solid heat-resistant, high-salt-resistant polymerizable macromonomer.

[0089] Example 5

[0090] 1. Inject N,N-dimethylethylenediamine into the first-stage M-type microfluidic reactor at a flow rate of 0.655 mL / min. Inject a tetrahydrofuran solution of 4-(methoxytriethyleneoxy)carboxybenzaldehyde into another inlet channel of the first-stage M-type microfluidic reactor at a flow rate of 6 mL / min. Control the heating module to maintain the reaction temperature at 30°C and the retention time is 9.02 min.

[0091] 2. The reaction product synthesized in step (1) is fed into a secondary M-type microfluidic reactor. Then, acrylic acid is injected into the secondary inlet of the second stage at a flow rate of 0.411 mL / min. The heating module is controlled to keep the reaction at 30°C and the retention time is 8.49 min.

[0092] 3. The reaction product synthesized in step (2) is fed into a three-stage M-type microfluidic reactor. Then, benzyl isonitrile is injected into the third-stage sub-inlet at a flow rate of 0.731 mL / min. The heating module is controlled to keep the reaction at 30°C and the retention time is 7.70 min.

[0093] 4. The reaction product synthesized in step (3) is fed into a four-stage M-type microfluidic reactor. At the same time, an aqueous solution of sodium 2-chloroethylsulfonate is fed into the fourth-stage auxiliary inlet at a flow rate of 6 mL / min. The heating module is controlled to keep the reaction at 80°C and the retention time is 4.35 min.

[0094] 5. The product solution produced at the outlet of the four-stage M-type microfluidic reactor is subjected to vacuum distillation to remove tetrahydrofuran and water, and then purified with a mixture of acetone and water to obtain a white solid heat-resistant, high-salt-resistant polymerizable macromonomer.

[0095] Table 1. Stability of solutions from Examples 1-5 after 90 days at 90°C

[0096]

[0097]

[0098] Examples 1-5: High-temperature salt resistance stability evaluation: using a salinity of 40919 mg / L (Ca) 2+ +Mg 2+ A 200 mg / L solution of the functional monomers from Examples 1-5 was prepared using simulated brine from a Bohai oilfield (1395 mg / L). Degassed crude oil from the Bohai oilfield was used, with a viscosity of 296.5 mPa·s. The interfacial tension between the functional monomers and the crude oil was measured at 90℃ and 6000 rpm. The evaluation results are shown in Table 1. After 90 days at 90℃, the interfacial tension remained almost unchanged, indicating that the functional monomers possess excellent stability under high temperature and high salinity conditions.

Claims

1. A heat-resistant, high-salt-resistant, highly surface-active polymerizable macromonomer, characterized in that: The heat-resistant, high-salt-resistant, highly surface-active, polymerizable macromonomer is any one of the following: 。 2. The continuous flow preparation method of the temperature-resistant, high-salt-resistant, highly surface-active polymerizable macromonomer according to claim 1, comprising the following steps in a expanding / shrinking M-type continuous flow microreactor: The structure of the expanding-contraction M-type continuous flow microreactor is as follows: Including the upper and lower substrates that fit together; The lower substrate is provided with an M-shaped main channel, one end of which is connected to a confluence channel and an inlet channel in sequence, and the other end is connected to an outlet channel; The upper substrate is provided with two inlets and one outlet, which are respectively connected to the inlet channel and the outlet channel; Several hybrid expansion and contraction units are arranged on the M-shaped main channel. The hybrid expansion and contraction unit refers to the structure formed by the inward bulge of the pipe wall of the M-shaped main channel. The four expanding-contraction M-type continuous flow microreactors are connected sequentially as a first-stage expanding-contraction M-type continuous flow microreactor, a second-stage expanding-contraction M-type continuous flow microreactor, a third-stage expanding-contraction M-type continuous flow microreactor, and a fourth-stage expanding-contraction M-type continuous flow microreactor, respectively, with the following connection relationships: The outlet of the first-stage expanding-shrink M-type continuous flow microreactor is connected to one of the inlets of the second-stage expanding-shrink M-type continuous flow microreactor, the outlet of the second-stage expanding-shrink M-type continuous flow microreactor is connected to one of the inlets of the third-stage expanding-shrink M-type continuous flow microreactor, and the outlet of the third-stage expanding-shrink M-type continuous flow microreactor is connected to one of the inlets of the fourth-stage expanding-shrink M-type continuous flow microreactor. S1. The amine and aldehyde are introduced into the inlet channel of the first-stage expanding-contracting M-type continuous flow microreactor at flow rates q1 and q2, respectively, and the reaction temperature is controlled at T1. The amine is N , N -Dimethylethylenediamine, 1-(3-aminopropyl)pyrrolidine or 4-amino-1-methylpiperidine; The aldehyde is 4-(methoxytriethyleneoxy)carboxybenzaldehyde; The temperature T1 is 25~45 °C; S2. The product obtained in step 1 is introduced through one of the inlets of the two-stage expansion-contraction M-type continuous flow microreactor, while the carboxylic acid is introduced through the other inlet of the two-stage expansion-contraction M-type continuous flow microreactor at a flow rate of q3, and the reaction temperature is controlled at T2. The carboxylic acid is C3-C. 17 alkenyl carboxylic acid; The T2 is 25~45 °C; S3. The product obtained in step 2 is introduced through one inlet of the three-stage expansion-contraction M-type continuous flow microreactor, and at the same time, isonitrile is introduced through the other inlet of the three-stage expansion-contraction M-type continuous flow microreactor at a flow rate of q4, and the reaction temperature is controlled at T3. The isonitrile is benzyl isonitrile or n-butyl isonitrile; The T3 is 25~45 °C; S4. The product obtained in step 3 is introduced into one inlet of the four-stage expansion-contraction M-type continuous flow microreactor, and at the same time, an aqueous solution of sodium 2-haloethyl sulfonate is introduced into the other inlet of the four-stage expansion-contraction M-type continuous flow microreactor at a flow rate of q5, and the reaction temperature is controlled at T4. The T4 temperature is 65~95 °C; S5. The product solution obtained from the outlet of the four-stage expansion-contraction M-type continuous flow microreactor is subjected to vacuum distillation to achieve continuous flow preparation of heat-resistant, high-salt-resistant, polymerizable macromonomers.

3. The continuous flow preparation method according to claim 2, characterized in that: In step S1, the flow rate q1 is 0.5~8 mL / min, and the flow rate q2 is 0.5~8 mL / min.

4. The continuous flow preparation method according to claim 2 or 3, characterized in that: In step S2, the flow rate q3 is 0.1~1 mL / min.

5. The continuous flow preparation method according to claim 2 or 3, characterized in that: In step S3, the flow rate q4 is 0.6~8 mL / min; In step S4, the sodium 2-haloethylsulfonate is sodium 2-chloroethylsulfonate or sodium 2-bromoethylsulfonate; the flow rate q5 is 1~8 mL / min.

6. The continuous flow preparation method according to claim 2 or 3, characterized in that: The molar ratio of the amine, the aldehyde, the carboxylic acid, the isonitrile, and the sodium 2-haloethylsulfonate is 1:0.8~1.2:1:0.8~1.2:1~1.

5.

7. The continuous flow preparation method according to claim 2 or 3, characterized in that: The M-shaped main channel is arranged in a serpentine pattern in the lower substrate.

8. The continuous flow preparation method according to claim 2 or 3, characterized in that: The corners of the M-shaped main channel are rounded.

9. The continuous flow preparation method according to claim 2 or 3, characterized in that: The hybrid expansion and contraction units are arranged periodically on the M-shaped main channel; The two adjacent hybrid expansion and contraction units are arranged in opposite directions and staggered. Each channel on the M-shaped main channel is provided with 3 to 4 of the aforementioned hybrid expansion and contraction units.

10. The continuous flow preparation method according to claim 2 or 3, characterized in that: The hybrid expansion and contraction unit includes a water-facing surface, a water-following surface, and a circular arc boundary; Both the water-facing surface and the water-following surface are tangentially connected to the circular arc boundary; The angle α between the upstream surface and the extended line of the M-shaped main channel is greater than the angle β between the downstream surface and the extended line of the M-shaped main channel. The radius of the arc angle formed by the connection between the upstream surface and the downstream surface is 38~42μm; The reduction ratio of the hybrid expansion and contraction unit for the M-shaped main channel is 73-77%.

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