Method for preparing polyolefin based on anionic polymerization of macro-micro reactor

Abstract

The invention discloses a method for preparing polyolefin based on anionic polymerization of a macro-micro reactor, which comprises the following step: in the macro-micro reactor, reacting an olefin monomer, an initiator and a solvent to obtain polyolefin and a copolymer thereof. According to the method, harsh reaction conditions of anionic polymerization can be effectively improved, and compared with a traditional synthesis method, the macro-micro reactor containing the internal component can remarkably shorten the reaction time of anionic polymerization, improve the conversion rate and reduce the reaction temperature. Compared with a traditional micro-reactor, by amplifying the size of the reactor and introducing a passively-reinforced internal component, the characteristic size of the macro-micro-reactor reaches the centimeter level, and high-flux synthesis is achieved. The invention provides a brand new thought for anionic polymerization, and has an industrial conversion prospect.

Description

Technical Field

[0001] The invention relates to the technical field of polymer synthesis, and in particular to a method for anionic polymerization based on macro- and micro-reactors. Background Art

[0002] This section merely provides background information related to the present disclosure and is not necessarily prior art.

[0003] Polyolefins have a wide range of industrial applications. Many commercial polymer polyolefins need to be achieved through anionic polymerization. In particular, butadiene-based polymers can be used to prepare rubber, adhesives, etc., and are used in the biomedical field as medical equipment shells, cling film, and disposable medical gloves. Many commercial polymers, such as polystyrene (PS), polymethyl methacrylate (PMMA) standard samples, and styrene-butadiene rubber (SBR), are produced through anionic polymerization, which is considered to be more ideal than free radical polymerization.

[0004] Anionic polymerization has a wide range of industrial application value. Many commercial polymers need to be realized through this method. In particular, butadiene-based polymers can be used to prepare rubber, adhesives, etc., and are used in the biomedical field as medical equipment shells, cling film, disposable medical gloves and other products. Anionic polymerization is based on the polymerization mechanism of fast initiation, slow growth, and no termination, which can achieve a faster polymerization rate and high monomer selectivity. However, the polymerization conditions are relatively harsh and are usually carried out at low temperatures. Trace impurities and interference from water and oxygen will lead to reaction termination. Szwarc discovered living anionic polymerization in 1956. This type of polymerization has no chain transfer and chain termination. During the polymerization process, the chain growth active center is relatively stable. By adjusting the reaction kinetics of initiation and growth, not only can the molecular weight of the product be effectively controlled, but also a polymerization product with an extremely narrow molecular weight distribution can be obtained. This type of reaction was first applied to a flow reactor in 1962. The anionic polymerization reported so far has high activity and high exothermic characteristics in its active centers in polar solvents and needs to be carried out at an extremely low temperature of -78°C, which seriously limits its industrialization; while the activity of the active centers in non-polar solvents is low, the reaction usually takes a long time and requires heating to proceed.

[0005] Szwarc discovered living anionic polymerization in 1956. This type of polymerization has no chain transfer or chain termination. During the polymerization process, the chain growth active center is relatively stable. By adjusting the reaction kinetics of initiation and growth, not only can the molecular weight of the product be effectively controlled, but also a polymerization product with an extremely narrow molecular weight distribution can be obtained. However, this type of polymerization has not yet been applied on a large scale in industry. It has the following main shortcomings and limitations: First, when anionic polymerization is carried out in a polar solvent in an intermittent reactor, the reaction needs to be carried out at a low temperature, such as -78°C. Secondly, when anionic polymerization is carried out in a non-polar solvent, the reaction takes a very long time to complete. Thirdly, anionic polymerization is very sensitive to water and oxygen, and usually requires an inert gas atmosphere such as argon to proceed smoothly.

[0006] The large specific surface area and continuous flow characteristics of the microreactor show the incomparable advantages of the kettle reactor in improving the harsh reaction conditions of anionic polymerization, regulating the molecular weight and distribution of the polymerization product, etc. Although many remarkable progress has been made in polymer synthesis through continuous flow living anionic polymerization, it also has quite obvious limitations: First, the microchannel reactor is theoretically amplified by orders of magnitude, and there will be no amplification effect, but this is not the case in actual operation. The flow pattern of the fluid in the microreactor is mostly laminar, and the mixing is basically controlled by the molecular diffusion between these thin layers. There is friction resistance between the fluid and the tube wall, which makes the fluid velocity near the tube wall slightly lower than the center of the fluid, forming a parabolic fluid pattern, resulting in an increase in the residence time distribution (RTD) and a corresponding widening of the molecular weight distribution of the resulting polymer. Secondly, because the microreactor is small in size, it is not conducive to the large-scale preparation of polymers, which greatly hinders industrial application. Summary of the invention

[0007] Purpose of the invention: The technical problem to be solved by the present invention is to provide a method for preparing polyolefins based on anionic polymerization in macro- and micro-reactors in view of the deficiencies in the prior art.

[0008] In order to solve the above technical problems, the present invention discloses the following technical solutions:

[0009] In a first aspect, the present invention discloses an application of a macro-micro reactor in the preparation of polyolefins and copolymers thereof.

[0010] The application is to prepare polyolefins and copolymers thereof using olefin monomers as raw materials; in some embodiments, the application is to react olefin monomers, initiators and solvents in macro-micro reactors to obtain polyolefins and copolymers thereof.

[0011] In a second aspect, the present invention discloses a method for preparing polyolefins and copolymers thereof based on macro-microreactors, that is, a method for anionic polymerization based on macro-microreactors.

[0012] The method comprises reacting olefin monomers, initiators and solvents in a macro-microreactor to obtain polyolefins and copolymers thereof; in some embodiments, the method comprises reacting a mixed solution containing olefins as polymerization monomers, butyl lithium (Bu-Li) as initiators and solvents in a macro-microreactor to obtain polyolefins and copolymers thereof.

[0013] In the above first and second aspects,

[0014] Wherein, the monomer is styrene, butadiene, or a combination of the two.

[0015] Wherein, the initiator is n-butyl lithium and sec-butyl lithium, preferably n-butyl lithium.

[0016] The molar ratio of the monomer to the initiator is 35-105:1. When the monomer is styrene, the molar ratio of the monomer to the initiator is 75-85:1, such as 80:1; when the monomer is butadiene, the molar ratio of the monomer to the initiator is 95-105:1, such as 100:1; when the monomer is a combination of styrene and butadiene, the molar ratio of styrene to the initiator is 35-45:1, such as 40:1.

[0017] In some embodiments, the reaction formula for preparing polystyrene using styrene or preparing polybutadiene using butadiene as a monomer is as follows:

[0018]

[0019] The number average molecular weight of the polystyrene is 8000-9500 g / mol, and the number average molecular weight of the polybutadiene is 5700-8500 g / mol.

[0020] In some embodiments, a polystyrene-block-polybutadiene polymer is prepared using styrene and butadiene as monomers, and the number average molecular weight of the polystyrene-block-polybutadiene polymer is 5000-6500 g / mol.

[0021] Wherein, the polybutadiene has different configurations, as shown in Table 1.

[0022] Table 1 Chemical shifts of various hydrogens in polybutadiene (PBd)

[0023]

[0024]

[0025] Wherein, when the olefin monomer is styrene, the solvent is a mixed solvent of tetrahydrofuran and cyclohexane, the volume ratio of tetrahydrofuran to cyclohexane is 1:2-4, preferably 1:2-3, and more preferably 1:3.

[0026] Wherein, when the olefin monomer is butadiene, the solvent is a mixed solvent of tetrahydrofuran, n-hexane and cyclohexane, the volume ratio of tetrahydrofuran:n-hexane:cyclohexane is 1:3-5:0-4, preferably 1:3-5:2-4, preferably 1:5:4.

[0027] Among them, when the olefin monomers are styrene and butadiene, the solvent is a mixed solvent of tetrahydrofuran, n-hexane and cyclohexane, the volume ratio of tetrahydrofuran, n-hexane and cyclohexane is 1:3-8:5-13, preferably 1:3-8:7-11, and further preferably 1:3-8:9.

[0028] The reaction feed method is two-stream feed or three-stream feed; the total flow rate of the reaction is 0.12-24 mL / min, and the reaction temperature is 15-35°C.

[0029] When the reaction is a two-stream feed, the reaction includes pumping the olefin monomer solution and the initiator solution into the mixer respectively and then flowing into the macro-micro reactor for reaction. When the olefin monomer is styrene, the solvent of the olefin monomer solution is a mixed solvent of tetrahydrofuran and cyclohexane, and the volume ratio of tetrahydrofuran to cyclohexane is 1:1-20; when the olefin monomer is butadiene, the solvent of the olefin monomer solution is a mixed solvent of tetrahydrofuran and n-hexane, and the volume ratio of tetrahydrofuran to n-hexane is 0.2-0.3:1. The concentration of the olefin monomer in the olefin monomer solution is 1.4-4 mol / L. The solvent of the initiator solution is cyclohexane; the concentration of the initiator in the initiator solution is 0.02-0.05 mol / L. The flow rate ratio of the olefin monomer solution and the initiator solution is 1-1.5:1. The flow rates of the olefin monomer solution and the initiator solution are independently selected from 6-12 mL / min.

[0030] When the reaction is a three-stream feed, the reaction includes pumping the first olefin monomer solution and the initiator solution into the first mixer at the same time, and then flowing into the first macro-micro reactor for the first reaction; the resulting effluent and the second olefin monomer solution are pumped into the second mixer at the same time, and then flowing into the second macro-micro reactor for the second reaction. The first olefin monomer and the second olefin monomer are independently selected from styrene and butadiene, respectively. In some embodiments, the first olefin monomer is styrene, and the second olefin monomer is butadiene. The solvent of the first olefin monomer solution is a mixed solvent of cyclohexane and tetrahydrofuran, and the volume ratio of cyclohexane to tetrahydrofuran is 1.5-5:1. The concentration of the first olefin monomer in the first olefin monomer solution is 1.5-2.5 mol / L. The solvent of the initiator solution is cyclohexane; the concentration of the initiator in the initiator solution is 0.02-0.05 mol / L. The solvent of the second monomer solution is n-hexane; the concentration of the second monomer in the second monomer solution is 1.7-2.1 mol / L. The flow rate ratio of the first olefin monomer solution, the initiator solution, and the second olefin monomer solution is 1:1:1. The flow rates of the first olefin monomer solution, the initiator solution, and the second olefin monomer solution are independently selected from 0.01-0.02 mL / min.

[0031] Wherein, after the reaction is completed, the reaction liquid is quenched, and the quenching technology is air quenching.

[0032] After the reaction is completed, the reaction solution is quenched and precipitated with a large amount of cold methanol, the product is collected by centrifugation, the product is dissolved in dichloromethane, and then precipitated and centrifuged again with cold methanol, and the process is repeated three times to fully wash the product. The washed product is placed in a vacuum drying oven and dried at 35° C. for 24 hours to obtain a polymer.

[0033] The macro-microreactor of the present invention comprises a microchannel pipeline (a spiral internal component microreactor), wherein a copper internal component is arranged inside the microchannel pipeline; the retention volume of the macro-microreactor is 2 to 50 mL, such as 5 mL; the inner diameter of the microchannel pipeline (a spiral internal component microreactor) is 3 to 10 mm; and the diameter of the copper internal component is 0.5 to 3 mm.

[0034] In some embodiments, the copper inner component is a spiral inner component, a serpentine inner component, an O-shaped inner component, or a linear inner component; the spiral inner component, the serpentine inner component and the O-shaped inner component have a pitch of 1 to 10 mm, such as 3-10 mm.

[0035] The polyolefin prepared by the method has a dispersion degree of 1.09-1.32.

[0036] The present invention uses macro-micro reactors to achieve better mixing during the reaction process, improve the mass transfer and heat transfer effect in the reactor, and conveniently and efficiently obtain a series of polyolefins, which can effectively shorten the reaction time, improve the conversion rate, and reduce the molecular weight distribution index, solving the problems of long reaction time and strict reaction conditions in the prior art. In addition, the present invention develops a continuous flow anionic polymerization platform. Through the study of polymerization reaction kinetics, the internal components can significantly expand the characteristic scale of the continuous flow reactor and expand the characteristic scale of the microreactor from hundreds of microns to centimeters, which can achieve high-throughput synthesis, large-scale preparation of polymers, and achieve efficient spatiotemporal control of polyolefin products, and promote the industrial application of anionic polymerization.

[0037] Compared with a typical microreactor (inner diameter = 1 mm), the conversion rate of the reaction using a continuous flow microreactor (inner diameter > 1 mm) is reduced, and the polymer molecular weight distribution index is increased. The present invention makes the macro-microreactor process enhancement effect similar to that of a typical microreactor by enlarging the reactor scale and introducing passively enhanced internal components. Further, by designing several macro-microreactors, it was found experimentally that the process enhancement effect of the spiral internal component microreactor is better than that of other internal component microreactors. The present invention provides a new idea for anion synthesis and fluid chemistry, and can effectively improve the harsh reaction conditions of anionic polymerization, and regulate the molecular weight and distribution of the polymerization product.

[0038] The present invention uses macro-micro reactors to achieve better mixing during the reaction process, improve the mass transfer and heat transfer effect in the reactor, and conveniently and efficiently obtain a series of polyolefins and their copolymers. By developing a continuous flow anionic polymerization platform and studying the polymerization reaction kinetics, it is found that the internal components can significantly expand the characteristic scale of the continuous flow reactor, reduce the product molecular weight distribution index, and achieve efficient spatiotemporal control of polyolefin products.

[0039] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0040] (1) The present invention is based on macro-microreactors to strengthen the anionic polymerization process and quickly and high-throughput prepare a series of polyolefins and their copolymers.

[0041] (2) Compared with the traditional tank reactor, the present invention significantly shortens the reaction time and improves the conversion rate based on the macro-micro reactor. For example, the anionic polymerization reaction time of styrene catalyzed by n-butyl lithium is shortened from 10 minutes to 25 seconds, and the conversion rate is increased from 90.7% to 97.1%. The molecular weight distribution index is reduced from 1.16 to 1.09.

[0042] (3) Compared with a typical microreactor (characteristic scale = 1.0 mm), the present invention significantly increases the reaction flux based on the macro-microreactor. For example, compared with Comparative Example 1 and Example 6, the flow rate is increased from 12 mL / min to 24 mL / min, and the output per unit time is increased from 2.14 g / min to 4.47 g / min.

[0043] (4) Compared with the continuous flow reactor (>2.0 mm without internal components), the present invention significantly improves the conversion rate and reduces the molecular weight distribution index based on the macro-micro reactor. For example, compared with Example 1, the conversion rate of the anionic polymerization reaction of styrene catalyzed by n-butyl lithium was increased from 71.6% to 97.1%, and the molecular weight distribution index was increased from 1.27 to 1.09. The number average molecular weight (M n,theo =8079 g / mol (macro-micro reactor) vs M n,GPC =9260 g / mol (macro-micro reactor)) ratio (M n,theo =5957 g / mol (continuous flow) vs M n,GPC =8140 g / mol (continuous flow)) is closer. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0045] Figure 1 Schematic diagram of the microreactor system used in this experiment.

[0046] Figure 2 For example 1 polystyrene 1 H-NMR spectrum.

[0047] Figure 3 For Example 12 polybutadiene 1 H-NMR spectrum.

[0048] Figure 4 Example 17 polystyrene-block-polybutadiene 1 H-NMR spectrum. DETAILED DESCRIPTION

[0049] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0050] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0051] In the following examples, a 400 MHz Bruker nuclear magnetic resonance instrument was used to 1 H NMR and 13 C NMR was used to characterize the structure of the polymerized product. 6 mg of the product was placed in a NMR tube, deuterated chloroform was added, and the sample was measured after shaking until it was completely dissolved.

[0052] The following examples were all carried out in a macro-microreactor system.

[0053] In some embodiments, the macro-microreactor system is Figure 1 As shown, the reaction device is composed of a Leifu injection pump, a first injector, a second injector, a mixer, a macro-micro reactor, a receiver and a magnetic heating stirrer. The first injector and the second injector are connected to the macro-micro reactor and the material receiving device in sequence through the mixer, and the macro-micro reactor is provided with a heating device. In some embodiments, the monomer styrene is mixed with the initiator butyl lithium in the mixer and fully reacted in the micro reaction channel. Wherein, the feed pump is connected to the injector respectively.

[0054] In some embodiments, the macro-micro reaction system includes a first injector, a second injector, a third injector, a first macro-micro reactor, a second macro-micro reactor and a material receiving device. The first injector and the second injector are connected to the first macro-micro reactor through a mixer, and the first macro-micro reactor and the third injector are connected to the second macro-micro reactor through a mixer, and then connected to the material receiving device in series. At the same time, the first macro-micro reactor and the second macro-micro reactor are both provided with a heating device.

[0055] like Figure 1 As shown: For macro-microreactor HSI (xxx), the first x represents the inner diameter of the reactor x mm (D), the second x represents the diameter of the spiral wire x mm (d4), and the third x represents the pitch x mm (l3). For macro-microreactor SLSI (xx), the first x represents the inner diameter of the reactor x mm (D), and the second x represents the diameter of the spiral wire x mm (d1). For macro-microreactor SSI (xxx), the first x represents the inner diameter of the reactor x mm (D), the second x represents the diameter of the spiral wire x mm (d2), and the third x represents the pitch x mm (l1). For macro-microreactor OSI (xxx), the first x represents the inner diameter of the reactor x mm (D), the second x represents the diameter of the spiral wire x mm (d3), and the third x represents the pitch x mm (l2).

[0056] Table 2 Various macro and micro reactor models in the examples

[0057]

[0058] Example 1

[0059] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium in cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (3-1-3, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate was 97.1% as measured by HNMR, and the theoretical molecular weight was 8079 g / mol. Subsequently, the reaction solution of 1 min 40 s (four cycles) was collected and poured into cold methanol for precipitation. After centrifugation, a white solid appeared at the bottom. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and the process was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene ( Figure 2 ), the number average molecular weight of polystyrene is 9260 g / mol, the molecular weight distribution index is 1.09, and the output per unit time is 2.18 g / min.

[0060] Example 2

[0061] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (2-0.5-1, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B=1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 25°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by HNMR was 97.3%, and the theoretical molecular weight was 8095 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. White solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8310 g / mol, the molecular weight distribution index was 1.14, and the output per unit time was 2.20 g / min.

[0062] Example 3

[0063] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (3-1-10, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 35°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by HNMR was 98.7%, and the theoretical molecular weight was 8212 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8620 g / mol, the molecular weight distribution index was 1.18, and the output per unit time was 2.23 g / min.

[0064] Example 4

[0065] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 41.52mL of styrene (360mmol), 20.79mL of cyclohexane, 27.69mL of tetrahydrofuran, and solution B: 1.8mL of sec-butyl lithium in cyclohexane (2.5mol / L, 4.5mmol) and 88.2mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (10-1.5-3, retention volume of 50mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the injection pump A flow rate: 6mL / min; injection pump B flow rate: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:4. At this time, the residence time of the reaction liquid in the micro-reaction channel is 250s, and the reaction is carried out at 15°C. After 500s (two cycles), a small amount of the reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by H NMR was 94.1%, and the theoretical molecular weight was 7829 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. White solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8160 g / mol, the molecular weight distribution index was 1.12, and the output per unit time was 2.12 g / min.

[0066] Example 5

[0067] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 41.52mL of styrene (360mmol), 2.31mL of cyclohexane, 46.17mL of tetrahydrofuran, solution B: 1.8mL of n-butyl lithium cyclohexane solution (2.5mol / L, 4.5mmol) and 88.2mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (10-3-5, retention volume of 50mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 12mL / min; the flow rate of injection pump B: 12mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:2. At this time, the residence time of the reaction liquid in the micro-reaction channel is 125s, and the reaction is carried out at 15°C. After 250s (two cycles), a small amount of the reaction liquid is taken and quenched in the air. 1The monomer conversion rate measured by HNMR was 97.1%, and the theoretical molecular weight was 8079 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. White solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8960 g / mol, the molecular weight distribution index was 1.32, and the output per unit time was 4.38 g / min.

[0068] Example 6

[0069] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (3-1-3, retention volume of 10mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 12mL / min; the flow rate of injection pump B: 12mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by HNMR was 99.1%, and the theoretical molecular weight was 8245 g / mol. Subsequently, the reaction solution was collected for 50 s (two cycles), poured into cold methanol for precipitation, and centrifuged to produce a white solid at the bottom. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol for washing, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene, with a number average molecular weight of 9460 g / mol, a molecular weight distribution index of 1.11, and a unit time output of 4.47 g / min.

[0070] Example 7

[0071] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 41.52mL of styrene (360mmol), 13.86mL of cyclohexane, 34.62mL of tetrahydrofuran, and solution B: 1.8mL of n-butyl lithium cyclohexane solution (2.5mol / L, 4.5mmol) and 88.2mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (10-3-5, retention volume of 50mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 12mL / min; the flow rate of injection pump B: 12mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 125s, and the reaction is carried out at 15°C. After 250s (two cycles), a small amount of the reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by HNMR was 99.1%, and the theoretical molecular weight was 8245 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. White solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 9160 g / mol, the molecular weight distribution index was 1.28, and the output per unit time was 4.48 g / min.

[0072] Example 8

[0073] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor SLSI (4-2, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1The monomer conversion rate measured by H NMR was 94.7%, and the theoretical molecular weight was 7879 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8360 g / mol, the molecular weight distribution index was 1.15, and the output per unit time was 2.14 g / min.

[0074] Example 9

[0075] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium in cyclohexane (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor SSI (D-1, 4-2-3, with a retention volume of 5mL) pipeline and equip them with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe pump A to 6mL / min; the flow rate of syringe pump B to 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by H NMR was 95.3%, and the theoretical molecular weight was 7929 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8270 g / mol, the molecular weight distribution index was 1.13, and the output per unit time was 2.15 g / min.

[0076] Example 10

[0077] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium in cyclohexane (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor SSI (D-2, 4-2-3, with a retention volume of 5mL) pipeline and equip them with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe pump A to 6mL / min; the flow rate of syringe pump B to 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by H NMR was 95.7%, and the theoretical molecular weight was 7962 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 9010 g / mol, the molecular weight distribution index was 1.12, and the output per unit time was 2.16 g / min.

[0078] Embodiment 11

[0079] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane, 11.54mL of tetrahydrofuran, and solution B: 0.6mL of n-butyl lithium cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor OSI (4-2-3, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1The monomer conversion rate measured by HNMR was 95.1%, and the theoretical molecular weight was 7912 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8710 g / mol, the molecular weight distribution index was 1.14, and the output per unit time was 218 g / min.

[0080] Example 12

[0081] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. Prepare solution A: 0.38mL cyclohexane solution of n-butyl lithium (2.5mol / L, 0.95mmol) and 39.62mL cyclohexane, and solution B: 50mL n-hexane solution of butadiene (1.9mol / L, 95mmol) and 10mL tetrahydrofuran in an argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the pipeline of the macro-microreactor HSI (3-1-3, with a retention volume of 5mL) and equip them with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 0.20mL / min, and the flow rate of syringe B (butadiene solution) to 0.30mL / min. After the two streams are mixed, the total flow rate of the reaction system is 0.5mL / min. At this time, the volume ratio of tetrahydrofuran, n-hexane and cyclohexane in the system was 1:5:4, and the retention time of all reactions was 10 min. The reaction system was carried out at 25 °C. After 20 min (two cycles), a small amount of the reaction solution was taken and quenched in the air. 1 The monomer conversion rate was 98.2% as measured by H NMR. The reaction solution was then taken, poured into cold methanol for precipitation, centrifuged, dissolved with a small amount of dichloromethane, and washed with cold methanol, which was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polybutadiene, with a number average molecular weight of 7410 g / mol, a molecular weight distribution index of 1.11, and a 1,2-configuration content of 90.5%.

[0082] Example 13

[0083] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water, and prepare solution A: 0.38mL cyclohexane solution of n-butyl lithium (2.5mol / L, 0.95mmol) and 39.62mL cyclohexane, solution B: 50mL n-hexane solution of butadiene (1.9mol / L, 95mmol) and 10mL tetrahydrofuran under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the pipeline of the macro-microreactor HSI (10-1.5-3, with a retention volume of 5mL) and equip them with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 0.20mL / min, and the flow rate of syringe B (butadiene solution) to 0.30mL / min. After the two streams are mixed, the total flow rate of the reaction system is 0.5mL / min. At this time, the volume ratio of tetrahydrofuran, n-hexane and cyclohexane in the system was 1:5:4, and the retention time of all reactions was 10 min. The reaction system was carried out at 15 °C, and after 20 min (two cycles), a small amount of the reaction solution was taken and quenched in the air. 1 The monomer conversion rate was measured by H NMR and was 91.1%. The reaction solution was then taken, poured into cold methanol for precipitation, centrifuged, dissolved with a small amount of dichloromethane, and washed with cold methanol, which was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polybutadiene, with a number average molecular weight of 5740 g / mol, a molecular weight distribution index of 1.10, and a 1,2-configuration content of 91.3%.

[0084] Embodiment 14

[0085] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water, and prepare solution A: 0.57mL cyclohexane solution of n-butyl lithium (2.5mol / L, 1.425mmol) and 59.43mL cyclohexane, solution B: 75mL n-hexane solution of butadiene (1.9mol / L, 142.5mmol) and 15mL tetrahydrofuran under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (10-3-5, retention volume of 50mL) spiral internal component reactor pipeline and equip with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 1mL / min, and the flow rate of syringe B (butadiene solution) to 1.5mL / min. After the two streams are mixed, the total flow rate of the reaction system is 2.5mL / min. At this time, the volume ratio of tetrahydrofuran, n-hexane and cyclohexane in the system was 1:5:4, and the retention time of all reactions was 20 min. The reaction system was carried out at 35 °C. After 40 min (two cycles), a small amount of the reaction solution was taken and quenched in the air. 1 The monomer conversion rate was 99.8% as measured by H NMR. The reaction solution was then taken, poured into cold methanol for precipitation, centrifuged, dissolved with a small amount of dichloromethane, and washed with cold methanol, which was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polybutadiene, with a number average molecular weight of 7760 g / mol, a molecular weight distribution index of 1.21, and a 1,2-configuration content of 83.5%.

[0086] Embodiment 15

[0087] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. Prepare solution A: 0.228mL cyclohexane solution of n-butyl lithium (2.5mol / L, 0.57mmol) and 19.772mL cyclohexane, solution B: 30mL n-hexane solution of butadiene (1.9mol / L, 57mmol) and 10mL tetrahydrofuran under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the macro-microreactor HSI (3-1-3, retention volume of 5mL) spiral internal component reactor pipeline and equip with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 0.2mL / min, and the flow rate of syringe B (butadiene solution) to 0.3mL / min. After the two streams are mixed, the total flow rate of the reaction system is 0.5mL / min. At this time, the volume ratio of tetrahydrofuran and cyclohexane in the system was 1:3:2, and the retention time of all reactions was 10 min. The reaction system was carried out at 25 °C, and after 20 min (two cycles), a small amount of the reaction solution was taken and quenched in the air. 1 The monomer conversion rate was 99.8% as measured by H NMR. The reaction solution was then collected for 40 minutes (four cycles), poured into cold methanol for precipitation, centrifuged, dissolved with a small amount of dichloromethane, and washed with cold methanol, which was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polybutadiene, with a number average molecular weight of 8060 g / mol, a molecular weight distribution index of 1.16, and a 1,2-configuration content of 88.5%.

[0088] Example 16

[0089] Take two 100mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. Prepare solution A: 0.38mL cyclohexane solution of n-butyl lithium (2.5mol / L, 0.95mmol) and 39.62mL cyclohexane, and solution B: 50mL n-hexane solution of butadiene (1.9mol / L, 95mmol) and 10mL tetrahydrofuran under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the pipeline of the macro-microreactor HSI (10-1.5-3, retention volume of 50mL) and equip with a syringe pump, and finally connect the microreactor to the material receiving device. Set the flow rate of syringe A (sec-butyl lithium solution) to 1mL / min, and the flow rate of syringe B (butadiene solution) to 1.5mL / min. After the two streams are mixed, the total flow rate of the reaction system is 2.5mL / min. At this time, the volume ratio of tetrahydrofuran and cyclohexane in the system was 1:5:4, and the retention time of all reactions was 20 min. The reaction system was carried out at 15 °C, and after 40 min (two cycles), a small amount of the reaction solution was taken and quenched in the air. 1 The monomer conversion rate was 95.1% as measured by H NMR. The reaction solution was then taken, poured into cold methanol for precipitation, centrifuged, dissolved with a small amount of dichloromethane, and washed with cold methanol, which was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polybutadiene, with a number average molecular weight of 7340 g / mol, a molecular weight distribution index of 1.18, and a 1,2-configuration content of 84.3%.

[0090] Embodiment 17

[0091] Two Schlenk glass reaction bottles with a volume of 100 mL are connected to the Schlenk device. While evacuating, the reaction bottle is evenly baked at high temperature using a Bunsen burner to remove water and oxygen. The reaction bottle is then passed through an inert gas and cooled to room temperature. After repeating the above baking and cooling process 3 times, the reaction bottle is cooled and sealed for standby use. Under an inert gas atmosphere in a glove box, 1.0 mL of a cyclohexane solution of n-butyl lithium (2.5 mmol) and 49 mL of cyclohexane are transferred to a reaction bottle. 11.7 mL of styrene (100 mmol), 29.5 mL of cyclohexane and 8.8 mL of tetrahydrofuran are added to another reaction bottle. After the two reaction bottles are sealed for the second time, a vortex oscillator is used to shake and the materials in the reaction bottle are fully mixed. In an anhydrous and oxygen-free environment in a glove box, syringes A, B, and C are rinsed three times with cyclohexane and tetrahydrofuran, respectively. Syringe A draws out all the cyclohexane solution of n-butyl lithium in the reaction bottle, syringe B draws out all the styrene solution, and syringe C draws out 50 mL of n-hexane solution of butadiene (1.9 mol / L). All syringes are cleared of bubbles and set aside.

[0092] Connect syringes A and B to the continuous flow pipeline and equip them with a syringe pump to complete the construction of the continuous flow reactor system. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 0.1mL / min, and the flow rate of syringe B (styrene solution) to 0.1mL / min. After the two streams are mixed, the total flow rate of the reaction system is 0.2mL / min. At this time, the volume ratio of solvent tetrahydrofuran and cyclohexane in the system is 1:9, and the reaction retention time of the first section R1 macro-microreactor HSI (3-1-3, retention volume is 2mL) is 10min. The reaction system is carried out at 25°C. After the reaction is carried out for 2 to 3 cycles, collect and quench 2mL of the reaction solution with a centrifuge tube filled with cold methanol to obtain a polystyrene precipitate. Collect 0.1mL of the reaction solution, immediately expose it to air for quenching, and carry out 1 H NMR characterization, the monomer conversion rate was measured to be 94.3%, and the remaining reaction liquid was treated to obtain a polystyrene number average molecular weight of 3923g / mol and a molecular weight distribution index of 1.24. Then, after the syringe C was assembled and connected to the first stage reaction tube, the flow rate was set to 0.1mL / min. At this time, the total flow rate in the second stage reaction tube R2 macro-microreactor HSI (3-1-3, retention volume of 3mL) was 0.3mL / min and the retention time was 10min. The reaction system was carried out at 25°C. After the second stage reaction was carried out for 2 to 3 cycles, the polystyrene-block-polybutadiene polymer was collected and characterized by NMR ( Figure 4 ), the conversion rate of butadiene monomer was measured to be 89.4%, and the product was subsequently collected by centrifugation, dissolved in dichloromethane, and centrifuged again with cold methanol for precipitation, which was repeated three times to fully wash the product. The pure product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain a polystyrene-block-polybutadiene polymer, the number average molecular weight of the polystyrene-block-polybutadiene polymer was 5958 g / mol, and the molecular weight distribution index was 1.28.

[0093] Embodiment 18

[0094] Two Schlenk glass reaction bottles with a volume of 100 mL are connected to the Schlenk device. While evacuating, the reaction bottle is evenly baked at high temperature using a Bunsen burner to remove water and oxygen. The reaction bottle is then passed through an inert gas and cooled to room temperature. After repeating the above baking and cooling process 3 times, the reaction bottle is cooled and sealed for standby use. Under an inert gas atmosphere in a glove box, 1.0 mL of a cyclohexane solution of n-butyl lithium (2.5 mmol) and 49 mL of cyclohexane are transferred to a reaction bottle. 11.7 mL of styrene (100 mmol), 23.6 mL of cyclohexane and 14.7 mL of tetrahydrofuran are added to another reaction bottle. After the two reaction bottles are sealed for the second time, a vortex oscillator is used to shake and the materials in the reaction bottle are fully mixed. In an anhydrous and oxygen-free environment in a glove box, syringes A, B, and C are rinsed three times with cyclohexane and tetrahydrofuran, respectively. Syringe A draws out all the cyclohexane solution of n-butyl lithium in the reaction bottle, syringe B draws out all the styrene solution, and syringe C draws out 50 mL of n-hexane solution of butadiene (1.9 mol / L). All syringes are cleared of bubbles and set aside.

[0095] Connect syringes A and B to the continuous flow pipeline and equip them with a syringe pump to complete the construction of the continuous flow reactor system. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 0.1mL / min, and the flow rate of syringe B (styrene solution) to 0.1mL / min. After the two streams are mixed, the total flow rate of the reaction system is 0.2mL / min. At this time, the volume ratio of solvent tetrahydrofuran and cyclohexane in the system is 1:5, and the reaction retention time of the first section R1 macro-microreactor HSI (3-1-3, retention volume is 2mL) is 10min. The reaction system is carried out at 25°C. After the reaction is carried out for 2 to 3 cycles, collect and quench 2mL of the reaction solution with a centrifuge tube filled with cold methanol to obtain a polystyrene precipitate. Collect 0.1mL of the reaction solution, immediately expose it to air for quenching, and carry out 1H NMR characterization, the monomer conversion rate was measured to be 99.6%, and the remaining reaction liquid was treated to obtain a polystyrene number average molecular weight of 4143g / mol and a molecular weight distribution index of 1.44. Then, after the syringe C was assembled and connected to the first stage reaction tube, the flow rate was set to 0.1mL / min. At this time, the total flow rate in the second stage reaction tube R2 macro-microreactor HSI (3-1-3, retention volume of 3mL) was 0.3mL / min, the retention time was 10min, and the reaction system was carried out at 25°C. After the second stage reaction was carried out for 2 to 3 cycles, the polystyrene-block-polybutadiene polymer was collected and characterized by nuclear magnetic resonance. The butadiene monomer conversion rate was measured to be 93.4%. The product was subsequently collected by centrifugation, dissolved in dichloromethane, and centrifuged again with cold methanol precipitation, and repeated three times to fully wash the product. The pure product was placed in a vacuum drying oven and dried at 35° C. for 48 hours to obtain a polystyrene-block-polybutadiene polymer. The number average molecular weight of the polystyrene-block-polybutadiene polymer was 6150 g / mol, and the molecular weight distribution index was 1.47.

[0096] Embodiment 19

[0097] Two Schlenk glass reaction bottles with a volume of 100 mL are connected to the Schlenk device. While evacuating, the reaction bottle is evenly baked at high temperature using a Bunsen burner to remove water and oxygen. The reaction bottle is then passed through an inert gas and cooled to room temperature. After repeating the above baking and cooling process 3 times, the reaction bottle is cooled and sealed for standby use. Under an inert gas atmosphere in a glove box, 1.0 mL of a cyclohexane solution of n-butyl lithium (2.5 mmol) and 49 mL of cyclohexane are transferred to a reaction bottle. 11.7 mL of styrene (100 mmol), 32.0 mL of cyclohexane and 6.3 mL of tetrahydrofuran are added to another reaction bottle. After the two reaction bottles are sealed for the second time, a vortex oscillator is used to shake and the materials in the reaction bottle are fully mixed. In an anhydrous and oxygen-free environment in a glove box, syringes A, B, and C are rinsed three times with cyclohexane and tetrahydrofuran, respectively. Syringe A draws out all the cyclohexane solution of n-butyl lithium in the reaction bottle, syringe B draws out all the styrene solution, and syringe C draws out 50 mL of n-hexane solution of butadiene (1.9 mol / L). All syringes are cleared of bubbles and set aside.

[0098] Connect syringes A and B to the continuous flow pipeline and equip them with a syringe pump to complete the construction of the continuous flow reactor system. Set the flow rate of syringe A (cyclohexane solution of n-butyl lithium) to 0.1mL / min, and the flow rate of syringe B (styrene solution) to 0.1mL / min. After the two streams are mixed, the total flow rate of the reaction system is 0.2mL / min. At this time, the volume ratio of solvent tetrahydrofuran and cyclohexane in the system is 1:13, and the reaction retention time of the first section R1 macro-microreactor HSI (3-1-3, retention volume is 2mL) is 10min. The reaction system is carried out at 25°C. After the reaction is carried out for 2 to 3 cycles, collect and quench 2mL of the reaction solution with a centrifuge tube filled with cold methanol to obtain a polystyrene precipitate. Collect 0.1mL of the reaction solution, immediately expose it to air for quenching, and carry out 1 H NMR characterization, the measured monomer conversion rate was 90.1%, and the remaining reaction liquid was treated to obtain a polystyrene number average molecular weight of 3748g / mol and a molecular weight distribution index of 1.21. Then, after the syringe C was assembled and connected to the first stage reaction tube, the flow rate was set to 0.1mL / min. At this time, the total flow rate in the second stage reaction tube R2 macro-microreactor HSI (3-1-3, retention volume of 3mL) was 0.3mL / min, the retention time was 10min, and the reaction system was carried out at 25°C. After the second stage reaction was carried out for 2 to 3 cycles, the polystyrene-block-polybutadiene polymer was collected and characterized by nuclear magnetic resonance. The butadiene monomer conversion rate was 84.4%. The product was subsequently collected by centrifugation, dissolved in dichloromethane, and centrifuged again with cold methanol precipitation, and repeated three times to fully wash the product. The pure product was placed in a vacuum drying oven and dried at 35° C. for 48 hours to obtain a polystyrene-block-polybutadiene polymer. The number average molecular weight of the polystyrene-block-polybutadiene polymer was 5480 g / mol, and the molecular weight distribution index was 1.31.

[0099] Comparative Example 1

[0100] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water, and prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane solution, 11.54mL of tetrahydrofuran solution, and solution B: 0.6mL of n-butyl lithium cyclohexane solution (2.5mol / L, 1.5mmol) and 29.4mL of cyclohexane under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the typical microreactor (inner diameter = 1mm, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B=1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by H NMR was 95.1%, and the theoretical molecular weight was 7912 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8160 g / mol, the molecular weight distribution index was 1.12, and the output per unit time was 2.14 g / min.

[0101] Comparative Example 2

[0102] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. Prepare solution A: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane solution, 11.54mL of tetrahydrofuran solution and 30mL of solution B (cyclohexane solution of n-butyl lithium, 0.05mol / L, 1.5mmol) respectively under argon atmosphere. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the continuous flow microreactor (inner diameter = 3mm, retention volume is 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by H NMR was 91.6%, and the theoretical molecular weight was 7621 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 9170 g / mol, the molecular weight distribution index was 1.18, and the output per unit time was 2.11 g / min.

[0103] Comparative Example 3

[0104] Take two 50mL Schlenk bottles, use double-row tubes to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, and prepare solution A under argon atmosphere: 13.84mL of styrene (120mmol), 4.62mL of cyclohexane solution, 11.54mL of tetrahydrofuran solution; solution B: (cyclohexane solution of n-butyl lithium, 0.05mol / L, 1.5mmol) 30mL. Then transfer the solutions to syringes A and B respectively, connect syringes A and B to the continuous flow microreactor (inner diameter = 10mm, retention volume of 5mL) pipeline and equip them with injection pumps, and finally connect the microreactor to the material receiving device. Set the flow rate of injection pump A: 6mL / min; the flow rate of injection pump B: 6mL / min, V A :V B =1:1, that is, the volume ratio of tetrahydrofuran to cyclohexane is 1:3. At this time, the residence time of the reaction liquid in the micro-reaction channel is 25s, and the reaction is carried out at 15°C. After 50s (two cycles), a small amount of reaction liquid is taken and quenched in the air. 1 The monomer conversion rate measured by H NMR was 71.6%, and the theoretical molecular weight was 5957 g / mol. The reaction solution was then taken and poured into cold methanol for precipitation. A white solid appeared at the bottom after centrifugation. The filter residue was collected, dissolved with a small amount of dichloromethane, precipitated with cold methanol and washed, and repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours to obtain polystyrene. The number average molecular weight of polystyrene was 8140 g / mol, the molecular weight distribution index was 1.27, and the output per unit time was 1.61 g / min.

[0105] Comparative Example 4

[0106] Take a 100mL Schlenk bottle, add a magnetic stirring rotor, use a double-row tube to evacuate the air in the bottle, add argon, repeat 3 times, and use a Bunsen burner to repeatedly bake to remove water and oxygen. While turning on the stirring, use a disposable syringe to add 30mL cyclohexane, 10mL tetrahydrofuran and the calculated amount of styrene monomer in sequence, and then cool the Schlenk bottle to 15°C in an ice salt bath. Absorb the calculated amount of n-butyl lithium so that [styrene St]0:[n-BuLi]0=80:1. Slowly add n-butyl lithium dropwise until the system changes from colorless to light yellow and does not fade for half a minute, then quickly add all the cyclohexane solution of n-butyl lithium at once. At this time, the reaction system is orange-red, indicating the presence of active chain ends. After 10 minutes, a small amount of reaction solution is aspirated in an argon atmosphere and quenched in the air, through 1H NMR measured the monomer conversion rate to be 90.7% and the theoretical molecular weight to be 7546 g / mol. A few drops of cold methanol were quickly added with a disposable injection needle, and the reaction solution immediately faded, indicating that the anionic polymerization process had terminated. The reaction solution was poured into cold methanol for precipitation and centrifugation, and a white solid appeared at the bottom. The filter residue was collected, dissolved with a small amount of dichloromethane, and washed with cold methanol, which was repeated three times. The product was placed in a vacuum drying oven at 30°C and dried for 24 hours. Polystyrene was obtained, and the number average molecular weight of polystyrene was 9110 g / mol and the molecular weight distribution index was 1.16.

[0107] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An application of a macro-micro reactor in the preparation of polyolefins and copolymers thereof; preferably, olefin monomers are used as raw materials to prepare polyolefins and copolymers thereof; preferably, olefin monomers, initiators and solvents are reacted in the macro-micro reactor to obtain polyolefins and copolymers thereof.

2. A method for preparing polyolefins and copolymers thereof based on macro-micro reactors, characterized in that: In a macro-micro reactor, olefin monomers, initiators and solvents are reacted to obtain polyolefins and copolymers thereof.

3. The use according to claim 1 or the method according to claim 2, characterized in that: The olefin monomer is styrene or butadiene; preferably, the initiator is butyl lithium; preferably, the initiator is n-butyl lithium or sec-butyl lithium.

4. The use according to claim 1 or the method according to claim 2, characterized in that: The olefin monomers are styrene and butadiene.

5. The use according to claim 1 or the method according to claim 2, characterized in that: When the olefin monomer is styrene, the solvent is a mixed solvent of tetrahydrofuran and cyclohexane, and the volume ratio of tetrahydrofuran to cyclohexane is 1:2-4, preferably 1:2-3, and further preferably 1:3; when the olefin monomer is butadiene, the solvent is a mixed solvent of tetrahydrofuran, n-hexane and cyclohexane, and the volume ratio of tetrahydrofuran:n-hexane:cyclohexane is 1:3-5:0-4, preferably 1:5:

4.

6. The use according to claim 1 or the method according to claim 2, characterized in that: When the olefin monomers are styrene and butadiene, the solvent is a mixed solvent of tetrahydrofuran, n-hexane and cyclohexane, and the volume ratio of tetrahydrofuran, n-hexane and cyclohexane is 1:3-8:5-13, preferably 1:3-8:7-11, and further preferably 1:3-8:

9.

7. The use according to claim 1 or the method according to claim 2, characterized in that: The reaction feeding method is two-stream feeding.

8. The use according to claim 1 or the method according to claim 2, characterized in that: The reaction feeding method is three-stream feeding.

9. The use according to claim 1 or the method according to claim 2, characterized in that: The total flow rate of the reaction is 0.12-24 mL / min; preferably, the temperature of the reaction is 15-35° C.; preferably, the inner diameter of the microreactor in the macro-microreactor is 3-10 mm, the diameter of the spiral internal component is 0.5-3 mm, and the pitch of the spiral internal component is 3-10 mm.

10. The use according to claim 1 or the method according to claim 2, characterized in that: The macro-microreactor comprises a microchannel pipeline, and a copper internal component is arranged inside the microchannel pipeline; the retention volume of the macro-microreactor is 2-50 mL; the inner diameter of the microchannel pipeline is 3-10 mm; the diameter of the copper internal component is 0.5-3 mm; preferably, the copper internal component is a spiral internal component, a serpentine internal component, an O-shaped internal component, or a linear internal component; the spiral internal component, the serpentine internal component and the O-shaped internal component have a pitch, and the pitch is 1-10 mm.

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