A method for radical polymerization based on macro-microreactor

Abstract

The application discloses a method based on macro-micro reactor free radical polymerization, and a polymethyl methacrylate and a copolymer thereof are obtained by reacting a methyl methacrylate monomer, an initiator, a ligand and a solvent in a macro-micro reactor. Compared with a traditional micro reactor, by enlarging the reactor scale and introducing passive reinforced inner members, the macro-micro reactor features a centimeter level, and high-throughput synthesis is realized. The application provides a technical scheme for copper catalyzed free radical polymerization, and has an industrial conversion prospect.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis technology, specifically relating to a method for free radical polymerization based on macro-micro reactors. Background Technology

[0002] Poly(meth)acrylate is an important polymer material with wide applications in medicine, coatings, construction, electronics, and other fields. With technological advancements and increasing demand for environmentally friendly materials, the application prospects of poly(meth)acrylate are becoming increasingly broad. Due to its excellent formability and processing properties, poly(meth)acrylate is indispensable in many fields. There are generally two methods for preparing poly(meth)acrylate: one is ionic polymerization, where methacrylate monomers undergo ionic polymerization under the action of a catalyst to form poly(meth)acrylate polymers, but this method generally requires high reaction temperatures and pressures. The other is free radical polymerization, where methacrylate monomers undergo free radical polymerization under the action of a free radical initiator to form poly(meth)acrylate polymers. This method is relatively simple, easy to implement, has high yields, and is suitable for large-scale production.

[0003] In recent years, copper(0)-mediated controlled radical polymerization (Cu(0)-RDRP) has attracted increasing attention. Copper(0)-mediated controlled radical polymerization is a living radical polymerization (LRP) using Cu(0) as the sole catalyst, capable of preparing various functional materials with high-fidelity radicals and low copper residue. Percec et al. termed it single-electron transfer living radical polymerization (SET-LRP), with the reaction mechanism involving Cu(0) activating the initiator haloalkane through an outer sphere electron transfer process, generating free radicals and Cu(I). Cu(I) then spontaneously disproportionates into Cu(0) (activator) and Cu(II) (deactivator). Some researchers have also explained this reaction mechanism using ATRP (SARA ATRP) with supplementary activators and reducing agents, but the two approaches remain controversial. Undeniably, Cu(0)-mediated reversible deactivating radical polymerization (RDRP) has become a useful and versatile tool for synthesizing polymers in aqueous and organic media, producing very well-defined materials, often with complex and well-designed macromolecular structures.

[0004] Microfluidic chemistry offers significant advantages over traditional batch reactors due to its large surface area to volume ratio and continuous flow characteristics. Traditional batch reactors suffer from limitations in mass and heat transfer and reaction control, and also have many inherent drawbacks, such as slow reaction rates, safety hazards, and difficulties in scale-up. To overcome these limitations, the application of microfluidic field technology (e.g., using microreactors to enhance mass and heat transfer) is urgently needed. Summary of the Invention

[0005] Purpose of the invention: The technical problem to be solved by the present invention is to provide a method for free radical polymerization based on macro-micro reactors, which addresses the shortcomings of the existing technology.

[0006] To address the aforementioned technical problems, this invention discloses a method for free radical polymerization based on macro / micro reactors, the specific technical solution of which is as follows:

[0007] In a first aspect, the present invention discloses the application of a macro / micro reactor in the preparation of poly(meth)acrylates and their copolymers.

[0008] The application is to prepare poly(meth)acrylate and its copolymers using (meth)acrylate monomers as raw materials; specifically, in a macro-micro reactor, (meth)acrylate monomers, initiators, ligands and solvents are reacted to obtain poly(meth)acrylate and its copolymers.

[0009] Secondly, the present invention discloses a method for preparing poly(meth)acrylate and its copolymers based on macro / micro reactors.

[0010] The method specifically involves reacting (meth)acrylate monomers, initiators, ligands, and solvents in a macro / micro reactor to obtain poly(meth)acrylates and their copolymers.

[0011] In the first and second aspects mentioned above,

[0012] The general formula for the reaction is as follows:

[0013]

[0014] The (meth)acrylate monomers include acrylate monomers and methacrylate monomers. The acrylate monomers are any one or a combination of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate (nBA), and tert-butyl acrylate (tBA), preferably methyl acrylate. The methacrylate monomers are any one or a combination of methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, and n-butyl methacrylate, preferably methyl methacrylate and glycidyl methacrylate.

[0015]

[0016] The initiator is any one or a combination of several of the following: ethyl α-bromoisobutyrate (EBIB), methyl α-bromophenylacetate (MBPA), ethyl α-bromophenylacetate (EBPA), methyl 2-bromopropionate (MBP), ethyl 2-bromopropionate (EBP), p-toluenesulfonyl chloride (TsCl), methyl 2-chloropropionate (MCP), 2,2-dichloroacetophenone (DCAP), ethyl 2-chloropropionate (ECP), and 2-chloropropionamide (CPA), preferably ethyl α-bromoisobutyrate.

[0017]

[0018] The ligand is any one of tris[2-(dimethylamino)ethyl]amine (Me6TREN), pentamethyldiethylenetriamine (PMDETA), and tris(2-pyridylmethyl)amine (TPMA), preferably tris[2-(dimethylamino)ethyl]amine.

[0019] The solvent is any one or a combination of several of tris(2,2,2-trifluoroethyl) phosphate, dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, and N,N-dimethylformamide, preferably dimethyl sulfoxide. The solution may also be any one or a combination of several of tris(2,2,2-trifluoroethyl) phosphate, dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, and N,N-dimethylformamide, or a mixture of any of the foregoing solvents and water, wherein the water content in the mixed solvent is 5-45% VT.

[0020] The molar ratio of the monomer to the initiator is 100-2500:1, preferably 1000-2500:1, and more preferably 1500:1; the molar ratio of the monomer to the ligand is 4000-10000:1, preferably 6000:1.

[0021] The solid content of the reaction is 20-60%, preferably 30-50%, and more preferably 40%. In this invention, the solid content is the ratio of the total mass of the monomer, initiator, and ligand to the total mass of the monomer, initiator, ligand, and solvent.

[0022] The reaction temperature is 20-60℃, preferably 20-40℃, and more preferably 30℃.

[0023] The flow rate of the reaction is 0.05-20 mL / min, preferably 0.2-20 mL / min, preferably 1-20 mL / min, preferably 5-20 mL / min, preferably 10-20 mL / min; preferably, the retention time of the reaction is 2.5-100 min, preferably 2.5-50 min, preferably 2.5-25 min.

[0024] The reaction of the present invention is carried out in a microreactor; the microreactor includes a feed pump, a copper pipe or a macro-microreactor with copper internal components, a heating device, and a receiver; wherein the copper pipe and the macro-microreactor are externally equipped with a heating device; the feed pump, the copper pipe or macro-microreactor, and the receiver are connected in sequence; the connection is a pipeline connection.

[0025] In some embodiments, the microreactor includes a feed pump, a macro-microreactor, and a receiver. In some embodiments, a single macro-microreactor is provided, with the feed pump, macro-microreactor, and receiver connected in sequence for preparing poly(meth)acrylate. In some embodiments, multiple macro-microreactors are provided, such as two macro-microreactors. The first feed pump and the first macro-microreactor are connected in series, the first macro-microreactor and the second feed pump are connected in parallel to the second macro-microreactor, and the second macro-microreactor and the receiver are connected in tandem for preparing poly(meth)acrylate copolymers. A heating device is provided externally for the macro-microreactor.

[0026] In some embodiments, a mixture containing (meth)acrylate monomers, an initiator, a ligand, and a solvent is passed through a macro-micro reaction to obtain poly(meth)acrylate. The molar ratio of the monomer to the initiator is 100-2500:1, preferably 1000-2500:1, more preferably 1500:1; the molar ratio of the monomer to the ligand is 4000-10000:1, preferably 6000:1; the solid content of the mixed solution is 20-60%, preferably 30-50%, more preferably 40%. The flow rate of the mixed solution is 0.2-20 mL / min, preferably 1-20 mL / min, preferably 5-20 mL / min, and preferably 10-20 mL / min.

[0027] In some embodiments, a first mixture containing a first (meth)acrylate monomer, an initiator, a ligand, and a first solvent is passed into a first macro-micro reaction to carry out a first reaction, yielding a first reaction effluent; a second mixture containing a second (meth)acrylate monomer and a second solvent is passed into a second macro-micro reaction with the first reaction effluent to carry out a second reaction, yielding a poly(meth)acrylate copolymer. The first (meth)acrylate monomer and the second (meth)acrylate monomer are different (meth)acrylate monomers. The first solvent and the second solvent may be the same or different. In the first mixture, the molar ratio of monomer to initiator is 100-2500:1, preferably 1000-2500:1, more preferably 1500:1; the molar ratio of monomer to ligand is 4000-10000:1, preferably 6000:1; the solid content of the first mixture is 20-60%, preferably 30-50%; and the flow rate of the first mixture is 0.05-20 mL / min. In the second mixed solution, the concentration of the monomer is 35-45%wt, preferably 41%wt; the mass ratio of the first (meth)acrylate monomer to the second (meth)acrylate monomer is 1-2:1, preferably 1.4:1; and the flow rate of the second mixed solution is 0.05-20mL / min.

[0028] In some embodiments, the macro-microreactor includes a channel shell and internal components within the channel shell. The retention volume of the macro-microreactor is 5-100 mL, such as 20, 25, or 50 mL. The internal components are helical, serpentine, straight, or O-shaped; the internal components are made of copper; the inner diameter of the channel shell is 2-10 mm, such as 3 or 5 mm; the diameter of the internal components is 0.5-3 mm; and the pitch of the helical, serpentine, and O-shaped internal components is independently selected from 1-10 mm, such as 3 mm. In some embodiments, the macro-microreactor includes a channel shell and helical internal components within the channel, wherein the helical internal components within the channel are made of copper. The macro-microreactor is prepared by inserting a centrally hollowed-out copper spiral (diameter 0.5-3 mm, pitch 1-10 mm) into a channel with an inner diameter of 2-10 mm.

[0029] The copper needs to be activated before each use. The copper is zero-valent copper. A preferred method is to use a syringe to draw 20 mL of dilute sulfuric acid solution and flush the pipeline at a flow rate of 0.333 mL / min for 60 min; then, draw another 20 mL of distilled water and flush the pipeline at a flow rate of 4 mL / min for 5 min to remove Cu₂O and CuO from the copper surface. Next, draw 20 mL of trifluoroethanol and flush the pipeline at a flow rate of 0.333 mL / min for 60 min to activate the copper. Finally, purge and dry the continuous flow reactor under a nitrogen atmosphere for 30 min to minimize oxygen in the system.

[0030] In some embodiments, after the reaction is completed, the reaction is quenched, the reaction solution is 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. This process is repeated three times to thoroughly wash the product. The washed product is placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain a pure polymer.

[0031] The quenching technology mentioned above is liquid nitrogen cryogenic quenching.

[0032] The dispersion of poly(meth)acrylate and its copolymers obtained by the above method is 1.1-1.4, such as 1.2, 1.25, and 1.3.

[0033] This invention improves mixing during the reaction process and enhances mass and heat transfer within the reactor by incorporating internal components into a microreactor, enabling the convenient and efficient production of a series of polyesters. A continuous-flow controllable free radical polymerization platform has been developed. Through research on polymerization kinetics, the internal components significantly expand the characteristic scale of the continuous-flow reactor, reduce the molecular weight distribution index of the products, and achieve efficient spatiotemporal control of the polyester products.

[0034] This invention extends the characteristic scale of microreactors from the hundreds of micrometers to the centimeter level through the design of internal components. By comparing it with hundreds-micrometer-scale microreactors, the enhancement effect of the internal component continuous flow reactor on the free radical polymerization process was studied, revealing a microscale effect similar to that of the hundreds-micrometer-scale microreactor. This effectively shortens the reaction time and reduces the molecular weight distribution index. Furthermore, the laboratory results from small-scale synthesis comprehensively reflect the actual situation of industrial processes, enabling the large-scale production of poly(meth)acrylates.

[0035] This invention demonstrates that, compared to a typical microreactor (inner diameter = 1 mm), using a continuous flow reactor (inner diameter > 1 mm) results in a lower reaction conversion rate and a higher polymer molecular weight distribution index. This invention, by scaling up the reactor scale and introducing passively reinforced internal components, achieves a process enhancement effect in the macro-(internal component) microreactor that is similar to or even better than that of a typical microreactor. Further experiments using several macro-microreactor designs revealed that the process enhancement effect of the helical internal component microreactor is superior to that of other internal component microreactors. Simultaneously, this method offers advantages such as simple operation, mild conditions, effective reduction of reaction time, and lower polymer molecular weight distribution index.

[0036] This invention utilizes macro- and microreactors for free radical polymerization, shortening the reaction time and increasing the conversion rate of copper-catalyzed free radical polymerization. Furthermore, by designing internal components, this invention extends the characteristic scale of the microreactor from the hundreds of micrometers to the centimeter level, enabling high-throughput synthesis and large-scale polymer preparation, thus promoting the industrial application of free radical polymerization.

[0037] The present invention provides a method for free radical polymerization based on macro-microreactors. The provided macro-microreactors can combine the microscale effect of microreactors at the hundred-micrometer level, extending the characteristic size of microreactors to the centimeter level. It can synthesize poly(meth)acrylates and their copolymers in high throughput, effectively solving the problems of reduced reaction conversion rate and increased polymer molecular weight distribution index in the existing continuous flow reactor (inner diameter > 1 mm), as well as the problem of long reaction time in the batch reactor.

[0038] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0039] (1) This invention is based on the enhanced copper-catalyzed free radical polymerization process using macro-micro reactors to rapidly and efficiently prepare poly(meth)acrylate and its copolymers.

[0040] (2) Compared with traditional batch reactors, this invention, based on a macro-micro reactor, significantly shortens the reaction time, increases the conversion rate, reduces the molecular weight distribution index, and improves the closeness between the actual number-average molecular weight and the theoretical molecular weight. For example, the reaction time for the free radical polymerization of methyl acrylate and ethyl α-bromoisobutyrate catalyzed by zero-valent copper is shortened from 100 min to 5 min, the conversion rate is increased from 47.4%-51.4% to 68.7%-75.4%, and the molecular weight distribution index is reduced from 1.25-1.26 to 1.10-1.1. The closeness between the actual number-average molecular weight and the theoretical number-average molecular weight in the macro-micro reactor (e.g., M...) is significantly improved. n,theo = 97266 g / mol (macro-micro reactor) vs M n,GPC =98820 g / mol (macro-micro reactor) This is closer to the actual number-average molecular weight than the theoretical number-average molecular weight in a batch reactor (e.g., M). n,theo=61146g / mol (stage) vs M n,GPC =71320g / mol (in batch) is closer.

[0041] (3) Compared with typical microreactors (characteristic scale = 1.0 mm), the present invention significantly increases the reaction flux based on macro-microreactors, for example, the flow rate is increased from 0.2 mL / min to 20 mL / min, the yield per unit time is increased from 0.047 g / min to 4.3817-5.8143 g / min, the conversion rate is increased from 63.8% to 65.4%-75.4%, and the molecular weight distribution index is reduced from 1.18 to 1.10-1.16.

[0042] (4) Compared with continuous flow reactors (>2.0 mm without internal components), this invention, based on a macro-micro reactor, significantly improves conversion rate, reduces molecular weight distribution index, and increases the closeness between actual and theoretical molecular weight. For example, the conversion rate of methyl acrylate to ethyl α-bromoisobutyrate free radicals catalyzed by zero-valent copper is increased from 50.1% to 68.7%-75.4%, and the molecular weight distribution index is reduced from 1.30 to 1.10-1.16. The closeness between actual and theoretical molecular weight in the macro-micro reactor (e.g., M...) is significantly improved. n,theo = 97461 g / mol (macro-micro reactor) vs M n,GPC =98820 g / mol (macro-micro reactor) The degree of closeness between the actual number-average molecular weight and the theoretical number-average molecular weight in a continuous flow reactor (M) n,theo =64629 g / mol (continuous flow) vs M n,GPC =69710 g / mol (continuous flow) is closer. Attached Figure Description

[0043] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0044] Figure 1 This is a schematic diagram of the microreactor system used in this experiment.

[0045] Figure 2 For example, polymethyl methacrylate (PMMA) of Example 1 1 H NMR spectrum.

[0046] Figure 3 Example 3: Polyglycidyl methacrylate 1 H NMR spectrum. Detailed Implementation

[0047] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0048] The following embodiments use a 400MHz Bruker nuclear magnetic resonance instrument. 1 H NMR and 13 The structure of the polymerization product was characterized by C10 NMR. 6 mg of poly(meth)acrylate sample was placed in an NMR tube, deuterated chloroform was added, and the mixture was shaken until completely dissolved before analysis.

[0049] The following embodiments are all performed in a macro-microreactor system. In some embodiments, the macro-microreactor system is as follows: Figure 1 As shown, the system includes a sample injection device connected to a macro-microreactor, which is equipped with a heating device, and then connected to a material receiving device. In some embodiments, the macro-microreactor system includes a first syringe, a second syringe, a first macro-microreactor, a second macro-microreactor, and a material receiving device. The first syringe is connected in sequence to the first macro-microreactor, and the first and second syringes are connected in parallel to the second macro-microreactor, which is then connected in sequence to the material receiving device. Both the first and second macro-microreactors are equipped with heating devices.

[0050] The following examples were all conducted in a macro-microreactor system. Figure 1 The macro-micro reactors shown in Table 1 are as follows: For the macro-micro reactor HSI(xxx), the first x represents the reactor inner diameter x mm (D), the second x represents the helix diameter x mm (d4), and the third x represents the pitch x mm (l3). For the macro-micro reactor SLSI(xx), the first x represents the reactor inner diameter x mm (D), and the second x represents the helix diameter x mm (d1). For the macro-micro reactor SSI(xxx), the first x represents the reactor inner diameter x mm (D), the second x represents the helix diameter x mm (d2), and the third x represents the pitch x mm (l1). For the macro-micro reactor OSI(xxx), the first x represents the reactor inner diameter x mm (D), the second x represents the helix diameter x mm (d3), and the third x represents the pitch x mm (l2).

[0051] Table 1

[0052]

[0053] In the following embodiments, W represents the solid content. Taking Example 1 as an example, the solid content = (90.363g of methyl acrylate + 0.1365g of EBiB + 0.0403g of Me6-TREN) / (135.8097g of dimethyl sulfoxide + 90.363g of methyl acrylate + 0.1365g of EBiB + 0.0403g of Me6-TREN) = 40%.

[0054] Example 1

[0055] A macro-microreactor (HSI 4-1-3, retention volume 100.00 mL) was used, and activated before each use. 90.363 g (1050 mmol) of methyl acrylate (MA), 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 75.4% by H NMR, and the theoretical molecular weight was 97461 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 98820 g / mol, the molecular weight distribution index was 1.10, and the yield per unit time was 5.8143 g / min. NMR results were as follows: Figure 2 As shown.

[0056] Example 2

[0057] The macro-microreactor HSI (4-1-3, retention volume 50 mL) was activated before each use. In a 100 mL reaction flask filled with inert gas, 30.116 g (300 mmol) of methyl methacrylate, 0.0458 g (0.2 mmol) of methyl α-bromophenylacetate, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 120.6932 g (W = 20%) of dimethyl sulfoxide (DMSO) were added. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred into the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 1 mL / min, i.e., the residence time was 50 min. The reaction temperature was 60 °C, and the reaction was started. After 100 min, the reaction solution was collected and quenched with liquid nitrogen. 1 HNMR analysis showed a conversion rate of 58.2% and a theoretical molecular weight of 87300 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl methacrylate (PMMA). The number-average molecular weight of PMMA was 87610 g / mol, the molecular weight distribution index was 1.18, and the yield per unit time was 0.1031 g / min.

[0058] Example 3

[0059] A macro-microreactor (HSI) of 10⁻¹⁵⁻³, with a retention volume of 100 mL, was activated before each use. 85.29 g (600 mmol) of glycidyl methacrylate, 0.1459 g (0.6 mmol) of ethyl α-bromophenylacetate, 0.0260 g (0.15 mmol) of pentamethyldiethylenetriamine (PMDETA), and 128.193 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 40 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1H NMR analysis showed a conversion rate of 68.7% and a theoretical molecular weight of 97657 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polyglycidyl methacrylate. The number-average molecular weight of polyglycidyl methacrylate was 98760 g / mol, the molecular weight distribution index was 1.19, and the yield per unit time was 5.4017 g / min. NMR data were as follows: Figure 3 As shown.

[0060] Example 4

[0061] A macro-microreactor (HSI) of 10⁻¹⁵⁻³, with a retention volume of 50 mL, was activated before each use. In a 100 mL reaction flask filled with inert gas, 34.242 g (300 mmol) of ethyl methacrylate, 0.0334 g (0.2 mmol) of methyl 2-bromopropionate, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 80 g (W = 30%) of 2,2,2-trifluoroethanol (TFE) were added. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred into the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 2 mL / min, i.e., the residence time was 25 min. The reaction temperature was 50 °C, and the reaction was started. After 50 min, the reaction solution was collected and quenched with liquid nitrogen. 1 HNMR analysis showed a conversion rate of 50.4% and a theoretical molecular weight of 86291 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polyethyl methacrylate. The number-average molecular weight of polyethyl methacrylate was 90870 g / mol, the molecular weight distribution index was 1.26, and the yield per unit time was 0.2780 g / min.

[0062] Example 5

[0063] A macro-microreactor (HSI 5-1.5-3, retention volume 25 mL) was used, and activated before each use. In a 100 mL reaction flask filled with inert gas, 30.12 g (300 mmol) of ethyl acrylate, 0.0362 g (0.2 mmol) of ethyl 2-bromopropionate, 0.0145 g (0.05 mmol) of tris(2-pyridylmethyl)amine (TPMA), and 70.3983 g (W = 30%) of N,N-dimethylformamide (DMF) were added. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred into the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 5 mL / min, i.e., the residence time was 5 min. The reaction temperature was 20 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 53.8% by ¹H NMR, and the theoretical molecular weight was 80700 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain ethyl polyacrylate. The number-average molecular weight of ethyl polyacrylate was 82780 g / mol, the molecular weight distribution index was 1.24, and the yield per unit time was 0.7451 g / min.

[0064] Example 6

[0065] A macro-microreactor (HSI, 10-3-10, retention volume 50 mL) was used, and activated before each use. 39.0425 g (300 mmol) of hydroxyethyl methacrylate, 0.0458 g (0.2 mmol) of methyl α-bromophenylacetate, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 91.2329 g (W = 30%) of isopropanol (IPA) were added to a 100 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 1 mL / min, i.e., the residence time was 50 min. The reaction temperature was 30 °C, and the reaction was started. After 100 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was 32.4% as determined by HNMR. The reaction solution was stored in vials for acetylation. To remove residual solvent more quickly, the polymer sample stored in the vial was dissolved in pyridine (0.5 mL pyridine / 20 mg polymer), followed by the addition of acetic anhydride (0.1 mL). The polymer was then precipitated in methanol. The precipitate was collected by centrifugation and washed several times with MeOH, dried, and dissolved in tetrahydrofuran for GPC analysis (relative to PMMA standard). The reaction solution was precipitated by adding cold methanol solution, centrifuged to collect the product, dissolved in dichloromethane, and then precipitated again by centrifugation with cold methanol. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35 °C for 48 h to obtain poly(hydroxyethyl methacrylate). The number-average molecular weight of poly(hydroxyethyl methacrylate) was 70190 g / mol, the molecular weight distribution index was 1.28, and the yield per unit time was 0.0897 g / min.

[0066] Example 7

[0067] The macro-microreactor HSI (2-0.5-1, retention volume 5 mL) was activated before each use. In a 100 mL reaction flask filled with inert gas, 34.836 g (300 mmol) of hydroxyethyl acrylate, 0.0390 g (0.2 mmol) of EBiB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 52.3298 g (W = 40%) of a methanol-water solution (40% H2O in MeOH) were added. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred into the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 1 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was 43.4% as determined by ¹H NMR. The residue was stored in vials for acetylation. To remove residual solvent more quickly, the polymer sample stored in the vials was dissolved in pyridine (0.5 mL pyridine / 20 mg polymer), followed by the addition of acetic anhydride (0.1 mL). The polymer was then precipitated in methanol. The precipitate was collected by centrifugation and washed several times with MeOH, dried, and dissolved in tetrahydrofuran for GPC analysis (relative to PMMA standards). The reaction solution was precipitated by adding cold methanol solution, centrifuged to collect the product, dissolved in dichloromethane, and then precipitated again by centrifugation with cold methanol. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35 °C for 48 h to obtain hydroxyethyl polyacrylate. The number-average molecular weight of hydroxyethyl polyacrylate was 60160 g / mol, the molecular weight distribution index was 1.28, and the yield per unit time was 0.1544 g / min.

[0068] Example 8

[0069] The macro-microreactor HSI (3-1-10, retention volume 50 mL) was activated before each use. 94.666 g (1100 mmol) of MA, 0.2146 g (1.1 mmol) of EBiB, 0.0634 g (0.275 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 63.296 g (W = 60%) of acetonitrile (MECN) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 5 mL / min, i.e., the residence time was 10 min. The reaction temperature was 30 °C, and the reaction was started. After 20 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 54.0% by ¹H NMR, and the theoretical molecular weight was 46440 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate (PMMA). The number-average molecular weight of PMMA was 45680 g / mol, the molecular weight distribution index was 1.27, and the yield per unit time was 1.4571 g / min.

[0070] Example 9

[0071] A macro-microreactor (HSI) of 10⁻³⁵, with a retention volume of 50 mL, was activated before each use. In a 250 mL reaction flask filled with inert gas, 42.6588 g (300 mmol) of n-butyl methacrylate, 0.0572 g (0.3 mmol) of p-toluenesulfonyl chloride, 0.0173 g (0.075 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 99.711 g (W = 30%) of an aqueous solution of tris(2,2,2-trifluoroethyl) phosphate (10% H₂O in TFP) were added. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred into the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 10 mL / min, i.e., the residence time was 5 min. The reaction temperature was 50 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was determined to be 49.3% by ¹H NMR, and the theoretical molecular weight was 70006 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain poly(n-butyl methacrylate). The number-average molecular weight of poly(glycidyl methacrylate) was 71760 g / mol, the molecular weight distribution index was 1.24, and the yield per unit time was 1.3091 g / min.

[0072] Example 10

[0073] The macro-microreactor HSI (4-1-3, retention volume 100 mL) was activated before each use. 94.666 g (1100 mmol) of MA, 0.0674 g (0.55 mmol) of MCP, 0.0317 g (0.1375 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 142.1477 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 55.4% by ¹H NMR, and the theoretical molecular weight was 95288 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate (PMMA). The number-average molecular weight of PMMA was 95680 g / mol, the molecular weight distribution index was 1.17, and the yield per unit time was 3.9814 g / min.

[0074] Example 11

[0075] The macro-microreactor HSI (4-1-3, retention volume 100 mL) was activated before each use. 94.666 g (1100 mmol) of MA, 0.0601 g (0.44 mmol) of ECP, 0.0253 g (0.11 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 142.1271 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 41.9% by ¹H NMR, and the theoretical molecular weight was 90085 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 91680 g / mol, the molecular weight distribution index was 1.16, and the yield per unit time was 2.9301 g / min.

[0076] Example 12

[0077] The macro-microreactor HSI (4-1-3, retention volume 100 mL) was activated before each use. 89.719 g (700 mmol) of n-butyl acrylate, 0.0883 g (0.467 mmol) of DCAP, 0.0269 g (0.11675 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 134.7513 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was determined to be 41.3% by ¹H NMR, and the theoretical molecular weight was 79401 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polybutylene acrylate (PMA). The number-average molecular weight of PMA was 81540 g / mol, the molecular weight distribution index was 1.17, and the yield per unit time was 2.8971 g / min.

[0078] Example 13

[0079] The macro-microreactor HSI (4-1-3, retention volume 100 mL) was activated before each use. 89.719 g (700 mmol) of tert-butyl acrylate, 0.0502 g (0.467 mmol) of CPA, 0.0269 g (0.11675 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 134.6942 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 44.7% by ¹H NMR, and the theoretical molecular weight was 85938 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain tert-butyl polyacrylate. The number-average molecular weight of tert-butyl polyacrylate was 87540 g / mol, the molecular weight distribution index was 1.18, and the yield per unit time was 3.0973 g / min.

[0080] Example 14

[0081] Both reactions were conducted using a macro-microreactor HSI (4-1-3, retention volume 5 mL), which was activated before each use. 42.645 g (300 mmol) of glycidyl methacrylate, 0.0390 g (0.2 mmol) of EBiB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 42.6955 g (W = 50%) of DMSO were added to a 100 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to syringe A of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 0.05 mL / min, i.e., the residence time was 100 min. The reaction temperature was 30 °C, and the reaction was started. After 200 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was 92.7% as determined by ¹H NMR. The number-average molecular weight of polyglycidyl methacrylate (PGMA) was 197,701 g / mol, and the molecular weight distribution index was 1.20. Subsequently, syringe B (42.7023 g DMSO and 30 g MMA) was connected to the macro-microreactor HSI, and the flow rate was set to 0.05 mL / min. At this point, the total flow rate in the second reaction tube was 0.1 mL / min, and the retention time was 50 min. After 100 min of reaction, a PMA-block-polymethyl methacrylate reaction solution was obtained. 1 The conversion rate was 52.7% as determined by HNMR. The number-average molecular weight of the polyglycidyl methacrylate-block-polymethyl methacrylate was 257,540 g / mol, and the molecular weight distribution index was 1.28.

[0082] Example 15

[0083] The macro-microreactor HSI (10⁻³⁵, retention volume 50 mL) was activated before each use. In a 100 mL reaction flask filled with inert gas, 25.818 g (300 mmol) of MA, 0.0390 g (0.2 mmol) of EBiB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 38.8028 g (W = 40%) of dimethyl sulfoxide (DMSO) were added. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred into the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 2.5 min. The reaction temperature was 30 °C, and the reaction was started. After 5 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was determined to be 50.3% by ¹H NMR, and the theoretical molecular weight was 65082 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 68820 g / mol, the molecular weight distribution index was 1.21, and the yield per unit time was 3.5013 g / min.

[0084] Example 16

[0085] The macro-microreactor SLSI (4-2, retention volume 100 mL) was activated before each use. 90.363 g (1050 mmol) of MA, 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 65.4% by ¹H NMR, and the theoretical molecular weight was 84561 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again by centrifugation with cold methanol, and this process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 85260 g / mol, the molecular weight distribution index was 1.16, and the yield per unit time was 4.7088 g / min.

[0086] Example 17

[0087] The macro-microreactor SSI (D-1, 4-2-3, retention volume 100 mL) was activated before each use. 90.363 g (1050 mmol) of MA, 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 71.1% by ¹H NMR, and the theoretical molecular weight was 91914 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again by centrifugation with cold methanol, and this process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 93700 g / mol, the molecular weight distribution index was 1.12, and the yield per unit time was 4.9172 g / min.

[0088] Example 18

[0089] The macro-microreactor SSI (D-2, 4-2-3, retention volume 100 mL) was activated before each use. 90.363 g (1050 mmol) of MA, 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was determined to be 71.3% by ¹H NMR, and the theoretical molecular weight was 92172 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again by centrifugation with cold methanol, and this process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 89870 g / mol, the molecular weight distribution index was 1.13, and the yield per unit time was 5.1348 g / min.

[0090] Example 19

[0091] The macro-microreactor OSI (4-2-3, retention volume 100 mL) was activated before each use. 90.363 g (1050 mmol) of MA, 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1 The conversion rate was determined to be 68.7% by ¹H NMR, and the theoretical molecular weight was 88818 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again by centrifugation with cold methanol, and this process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 89830 g / mol, the molecular weight distribution index was 1.15, and the yield per unit time was 4.3817 g / min.

[0092] Example 20

[0093] The macro-microreactor HSI (4-1-3, retention volume 5 mL) was activated before each use. 25.818 g (300 mmol) of MA, 0.0390 g (0.2 mmol) of EBiB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 38.8028 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 100 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 0.2 mL / min, i.e., the residence time was 25 min. The reaction temperature was 30 °C, and the reaction was started. After 50 min, the reaction solution was collected and quenched with liquid nitrogen. 1 ¹H NMR analysis showed a conversion rate of 60.4% and a theoretical molecular weight of 77970 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate (PMMA). The number-average molecular weight of PMMA was 79820 g / mol, the molecular weight distribution index was 1.17, and the yield per unit time was 0.043 g / min.

[0094] Comparative Example 1

[0095] In a typical microreactor (with an inner diameter of 1 mm and a retention volume of 5.00 mL using copper tubing), the continuous flow microreactor was activated before each use. 25.818 g (300 mmol) of MA, 0.0458 g (0.2 mmol) of EBIB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 38.8130 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 100 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 0.2 mL / min, i.e., the residence time was 25 min. The reaction temperature was 30 °C, and the reaction was started. After 50 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was determined to be 63.8% by ¹H NMR, and the theoretical molecular weight was 82497 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate (PMMA). The number-average molecular weight of PMMA was 87490 g / mol, the molecular weight distribution index was 1.18, and the yield per unit time was 0.047 g / min.

[0096] Comparative Example 2

[0097] In a typical microreactor (with an inner diameter of 1 mm and a retention volume of 100.00 mL using copper tubing), the continuous flow microreactor was activated before each use. 90.363 g (1050 mmol) of MA, 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was then connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. An instrument alarm was triggered during the reaction, indicating that no reaction solution was flowing out.

[0098] Comparative Example 3

[0099] The continuous flow microreactor (inner diameter = 4 mm, retention volume = 100.00 mL copper tube) was activated before each use. 90.363 g (1050 mmol) of MA, 0.1365 g (0.7 mmol) of EBiB, 0.0403 g (0.175 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097 g (W = 40%) of dimethyl sulfoxide (DMSO) were added to a 250 mL reaction flask filled with inert gas. After the addition was complete, the reaction solution was deoxygenated. The solution from the reaction flask was transferred to the syringe of the injection device, which was connected to the injection pump and the continuous flow system. The flow rate was set to 20 mL / min, i.e., the residence time was 5 min. The reaction temperature was 30 °C, and the reaction was started. After 10 min, the reaction solution was collected and quenched with liquid nitrogen. 1The conversion rate was determined to be 50.1% by ¹H NMR, and the theoretical molecular weight was 64824 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, it was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 69710 g / mol, the molecular weight distribution index was 1.30, and the yield per unit time was 3.6172 g / min.

[0100] Comparative Example 4

[0101] In a 100 mL reaction flask filled with inert gas, add 25.818 g (300 mmol) of MA, 0.0390 g (0.2 mmol) of EBiB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), 40 mg of activated copper powder, and 38.8028 g (W = 40%) of dimethyl sulfoxide (DMSO). After the addition is complete, the reaction solution is deoxygenated. The reaction time is 100 min. The reaction temperature is 30 °C. After 100 min, the reaction solution is quenched with liquid nitrogen. 1 The conversion rate was determined to be 51.4% by ¹H NMR, and the theoretical molecular weight was 66306 g / mol. The reaction solution was precipitated with cold methanol solution, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was precipitated again with cold methanol and centrifuged. This process was repeated three times to thoroughly wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate. The number-average molecular weight of polymethyl acrylate was 71820 g / mol, the molecular weight distribution index was 1.25, and the yield per unit time was 0.0107 g / min.

[0102] Comparative Example 5

[0103] In a 100 mL reaction flask filled with inert gas, add 25.818 g (300 mmol) of MA, 0.0390 g (0.2 mmol) of EBiB, 0.0115 g (0.05 mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 38.8028 g (W = 40%) of dimethyl sulfoxide (DMSO). After the addition is complete, a 1 mm copper wire (activated) is attached to a magnetic stir bar for stirring, and the reaction solution is deoxygenated. The reaction time is 100 min. The reaction temperature is 30 °C. After 100 min, the reaction solution is quenched with liquid nitrogen. 1HNMR analysis revealed a conversion rate of 47.4% and a theoretical molecular weight of 61146 g / mol. The reaction solution was precipitated with cold methanol, and the product was collected by centrifugation. After dissolving the product in dichloromethane, the product was again precipitated and centrifuged with cold methanol, repeated three times to thoroughly wash the product. The washed product was then placed in a vacuum drying oven and dried at 35°C for 48 h to obtain polymethyl acrylate (PMMA). The number-average molecular weight of PMMA was 71320 g / mol, the molecular weight distribution index was 1.26, and the yield per unit time was 0.0987 g / min.

[0104] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. The application of a macro-microreactor in the preparation of polymethacrylate and its copolymers, characterized in that, In a macro-microreactor, methacrylate monomers, initiators, ligands, and solvents are reacted to obtain polymethacrylate and its copolymers. The macro-microreactor includes a channel shell and internal components within the channel shell. The internal components are helical, serpentine, or linear. The internal components are made of copper. The inner diameter of the channel shell is 3-10 mm, and the diameter of the internal components is 0.5-3 mm. The pitch of the helical and serpentine internal components is independently selected from 3-10 mm.

2. The application according to claim 1, characterized in that, The methacrylate monomer is any one or a combination of methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate; the initiator is any one or a combination of ethyl α-bromoisobutyrate, methyl α-bromophenylacetate, ethyl α-bromophenylacetate, methyl 2-bromopropionate, and ethyl 2-bromopropionate; the ligand is any one of tris[2-(dimethylamino)ethyl]amine, pentamethyldiethylenetriamine, and tris(2-pyridylmethyl)amine; and the solvent is any one or a combination of dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, and N,N-dimethylformamide.

3. The application according to claim 1, characterized in that, The reaction temperature is 20-60 °C; the solid content of the reaction is 20-60%; and the molar ratio of the monomer to the initiator is 100-2500:

1.

4. The application according to claim 1, characterized in that, The reaction temperature is 20-40℃; the solid content of the reaction is 30-50%; and the molar ratio of the monomer to the initiator is 1000-2500:

1.

5. The application according to claim 1, characterized in that, The reaction temperature is 30°C; the solid content of the reaction is 40%; and the molar ratio of the monomer to the initiator is 1500:

1.

6. The application according to claim 1, characterized in that, The flow rate of the reaction is 0.2-20 mL / min; the retention time of the reaction is 2.5-100 min.

7. A method for preparing polymethacrylate and its copolymers based on macro-microreactors, characterized in that, In a macro-microreactor, methacrylate monomers, initiators, ligands, and solvents are reacted to obtain polymethacrylate and its copolymers. The macro-microreactor includes a channel shell and internal components within the channel shell. The internal components are helical, serpentine, or linear. The internal components are made of copper. The inner diameter of the channel shell is 3-10 mm, and the diameter of the internal components is 0.5-3 mm. The pitch of the helical and serpentine internal components is independently selected from 3-10 mm.

8. The method according to claim 7, characterized in that, The methacrylate monomer is any one or a combination of methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate; the initiator is any one or a combination of ethyl α-bromoisobutyrate, methyl α-bromophenylacetate, ethyl α-bromophenylacetate, methyl 2-bromopropionate, and ethyl 2-bromopropionate; the ligand is any one of tris[2-(dimethylamino)ethyl]amine, pentamethyldiethylenetriamine, and tris(2-pyridylmethyl)amine; and the solvent is any one or a combination of dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, and N,N-dimethylformamide.

9. The method according to claim 7, characterized in that, The reaction temperature is 20-60℃; the solid content of the reaction is 20-60%; and the molar ratio of the monomer to the initiator is 100-2500:

1.

10. The method according to claim 7, characterized in that, The reaction temperature is 20-40℃; the solid content of the reaction is 30-50%; and the molar ratio of the monomer to the initiator is 1000-2500:

1.

11. The method according to claim 7, characterized in that, The reaction temperature is 30°C; the solid content of the reaction is 40%; and the molar ratio of the monomer to the initiator is 1500:

1.

12. The method according to claim 7, characterized in that, The flow rate of the reaction is 0.2-20 mL / min; the retention time of the reaction is 2.5-100 min.

13. A method for preparing polyacrylates and their copolymers based on macro- and micro-reactors, characterized in that, In a macro-microreactor, acrylate monomers, initiators, ligands, and solvents are reacted to obtain polyacrylates and their copolymers. The macro-microreactor includes a channel shell and internal components within the channel shell. The internal components are spiral, serpentine, or straight. The internal components are made of copper. The inner diameter of the channel shell is 3-10 mm, and the diameter of the internal components is 0.5-3 mm. The pitch of the spiral and serpentine internal components is independently selected from 3-10 mm.

14. The method according to claim 13, characterized in that, The acrylate monomer is any one or a combination of methyl acrylate, ethyl acrylate, and hydroxyethyl acrylate; the initiator is any one or a combination of ethyl α-bromoisobutyrate, methyl α-bromophenylacetate, ethyl α-bromophenylacetate, methyl 2-bromopropionate, and ethyl 2-bromopropionate; and the ligand is any one of tris[2-(dimethylamino)ethyl]amine, pentamethyldiethylenetriamine, and tris(2-pyridylmethyl)amine.

15. The method according to claim 13, characterized in that, The molar ratio of the monomer to the initiator is 100-2500:1; the solid content of the reaction is 20-60%; the reaction temperature is 20-60 °C; the reaction flow rate is 0.2-20 mL / min; and the reaction retention time is 2.5-100 min.

16. The method according to claim 13, characterized in that, The molar ratio of the monomer to the initiator is 1000-2500:1; the solid content of the reaction is 30-50%; and the reaction temperature is 20-40 °C.

17. The method according to claim 13, characterized in that, The molar ratio of the monomer to the initiator is 1500:1; the solid content of the reaction is 40%; and the reaction temperature is 30 °C.

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