Free radical polymerization method based on macro-micro reactor

Abstract

The invention discloses a free radical polymerization method based on a macro-micro reactor, which comprises the following step: in the macro-micro reactor, reacting a methacrylate monomer with an initiator, a ligand and a solvent to obtain polymethacrylate and a copolymer thereof. 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 technical scheme for copper-catalyzed free radical polymerization and has an industrial conversion prospect.

Description

Technical Field

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

[0002] Poly(meth)acrylate is an important polymer material with a wide range of applications in the fields of medicine, coatings, construction, electronics, etc. With the advancement of science and technology and people's demand for environmentally friendly materials, the application prospects of poly(meth)acrylate will become increasingly broad. Since poly(meth)acrylate has good formability and processing characteristics, it is indispensable in many fields. There are generally two methods for preparing poly(meth)acrylate. One is the ion polymerization method, in which (meth)acrylate monomers undergo ion polymerization under the action of a catalyst to form a poly(meth)acrylate polymer, but this method generally requires a higher reaction temperature and pressure. The other is the free radical polymerization method, in which (meth)acrylate monomers undergo free radical polymerization under the action of a free radical initiator to form a poly(meth)acrylate polymer. This method is relatively simple and easy to operate, has a high yield, 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) with Cu(0) as the sole catalyst, which can prepare various functional materials under conditions such as high radical fidelity and low copper residue. Percec et al. called it single electron transfer living radical polymerization (SET-LRP). The reaction mechanism is that Cu(0) activates the initiator halogenated alkane through an outer sphere electron transfer process to generate free radicals and Cu(I), and Cu(I) spontaneously disproportionates to Cu(0) (activator) and Cu(II) (deactivator). Some researchers also explain it with the reaction mechanism of ATRP (SARA ATRP) supplemented with activator and reductant, and there is constant controversy between the two. It is undeniable that Cu(0)-mediated reversible deactivation 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 designed macromolecular structures.

[0004] Microfluidic chemistry has significant advantages over traditional tank reactions due to its huge surface area to volume ratio and continuous flow characteristics. When traditional tank reactors are used for chemical reactions, there are limitations in mass transfer, heat transfer, and reaction control, and they themselves have many disadvantages, such as slow reaction rates, safety hazards, and difficulty in process scale-up. In order to overcome the limitations of the above-mentioned tank reactor method, microfluidic field technology (such as the use of microreactors to enhance mass transfer 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 in view of the deficiencies in the prior art.

[0006] In order to solve the above technical problems, the present invention discloses a method for free radical polymerization based on macro-micro reactors, and the specific technical scheme is as follows:

[0007] In a first aspect, the present invention discloses an application of a macro-microreactor in the preparation of poly(meth)acrylate and its copolymer.

[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 are reacted with an initiator, a ligand and a solvent to obtain poly(meth)acrylate and its copolymers.

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

[0010] The method specifically comprises reacting (meth)acrylate monomers with an initiator, a ligand and a solvent in a macro-microreactor to obtain poly(meth)acrylate and a copolymer thereof.

[0011] In the above first and second aspects,

[0012] Wherein, the reaction formula is as follows:

[0013]

[0014] Wherein, the (meth)acrylate monomers include acrylate monomers and methacrylate monomers. Wherein, 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. Wherein, 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] Wherein, the initiator is any one or a combination of 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] Wherein, the ligand is any one of tris[2-(dimethylamino)ethyl]amine (Me6TREN), pentamethyldiethylenetriamine (PMDETA), tris(2-pyridylmethyl)amine (TPMA), preferably tris[2-(dimethylamino)ethyl]amine.

[0019] Wherein, the solvent is any one or a combination of tris(2,2,2-trifluoroethyl) phosphate, dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, N,N-dimethylformamide, preferably dimethyl sulfoxide. The solution can also be any one or a combination of tris(2,2,2-trifluoroethyl) phosphate, dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, N,N-dimethylformamide, or a mixed solvent of any one of the foregoing and water, and 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, and preferably 6000:1.

[0021] The solid content of the reaction is 20-60%, preferably 30-50%, and more preferably 40%. The solid content in the present invention is the ratio of the total mass of monomers, initiators, and ligands to the total mass of monomers, initiators, ligands, and solvents.

[0022] Wherein, the reaction temperature is 20-60°C, preferably 20-40°C, and more preferably 30°C.

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

[0024] The reaction of the present invention is carried out in a micro-reactor; the micro-reactor comprises a feed pump, a copper tube or a macro-micro reactor with copper internal components, a heating device and a receiver; wherein the copper tube and the macro-micro reactor are provided with a heating device outside; the feed pump, the copper tube or the macro-micro reactor and the receiver are connected in sequence; and the connection is a pipeline connection.

[0025] In some embodiments, the micro-reactor comprises a feed pump, a macro-microreactor and a receiver. In some embodiments, a macro-microreactor is provided, and the feed pump, the macro-microreactor and the receiver are connected in sequence for preparing poly(meth)acrylate. In some embodiments, a plurality of macro-microreactors are provided, such as two macro-microreactors, the first feed pump and the first macro-microreactor are connected in series in sequence, the first macro-microreactor and the second feed pump are connected in parallel to the second macro-microreactor, and the second macro-microreactor is connected in series with the receiver for preparing poly(meth)acrylate copolymer. A heating device is provided outside the macro-microreactor.

[0026] In some embodiments, a mixed solution containing (meth)acrylate monomers, initiators, ligands and solvents is passed into a macro-micro reaction to react and obtain poly(meth)acrylate. 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, and more preferably 6000:1; the solid content of the mixed solution is 20-60%, preferably 30-50%, and more preferably 40%. The flow rate of the mixed solution is 0.2-20mL / min, preferably 1-20mL / min, preferably 5-20mL / min, and more preferably 10-20mL / min.

[0027] In some embodiments, a first mixed solution containing a first (meth)acrylate monomer, an initiator, a ligand, and a first solvent is passed into a first macro-micro reaction to perform a first reaction to obtain a first reaction effluent; a second mixed solution containing a second (meth)acrylate monomer and a second solvent is passed into a second macro-micro reaction with the first reaction effluent to perform a second reaction to obtain 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 mixed solution, the molar ratio of the monomer to the initiator is 100-2500:1, preferably 1000-2500:1, and further preferably 1500:1; the molar ratio of the monomer to the ligand is 4000-10000:1, preferably 6000:1; the solid content of the first mixed solution is 20-60%, preferably 30-50%; the flow rate of the first mixed solution is 0.05-20mL / 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; 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 an internal member in the channel shell. The retention volume of the macro-microreactor is 5-100mL, such as 20, 25, 50mL. The internal member is a spiral internal member, a serpentine internal member, a linear internal member or an O-shaped internal member; the internal member is a copper internal member; the inner diameter of the channel shell is 2-10mm, such as 3, 5mm, the diameter of the internal member is 0.5-3mm, and the pitch of the spiral internal member, the serpentine internal member, and the O-shaped internal member is independently selected from 1-10mm, such as 3mm. In some embodiments, the macro-microreactor includes a channel shell and a spiral internal member in the channel, and the material of the spiral internal member in the channel is copper. Wherein, the preparation method of the macro-microreactor is: a copper spiral with a hollow center (diameter of 0.5-3mm, pitch of 1-10mm) and an inner diameter of 2-10mm in the channel.

[0029] Copper needs to be activated before each use. The copper is zero-valent copper. The preferred method is to draw 20 mL of dilute sulfuric acid solution with a syringe and flush the pipeline at a flow rate of 0.333 mL / min for 60 minutes; then, draw another 20 mL of distilled water at a flow rate of 4 mL / min to flush the pipeline for 5 minutes to remove Cu2O and CuO on the copper surface. Draw 20 mL of trifluoroethanol again and flush the pipeline at a flow rate of 0.333 mL / min for 60 minutes to activate the copper. Finally, the continuous flow reactor is purged and dried under N2 atmosphere for 30 minutes to minimize the oxygen in the system.

[0030] In some embodiments, after the reaction is completed, the reaction solution is quenched, and the reaction solution is precipitated with a large amount of cold methanol, and the product is collected by centrifugation. After the product is dissolved in dichloromethane, it is 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 48 hours to obtain a pure polymer.

[0031] Wherein, the quenching technology is liquid nitrogen freezing quenching.

[0032] The poly(meth)acrylate and copolymers thereof prepared by the method have a dispersity of 1.1-1.4, such as 1.2, 1.25, and 1.3.

[0033] The present invention achieves better mixing during the reaction process by placing internal components into the microreactor, and improves the mass transfer and heat transfer effect in the reactor, so as to obtain a series of polyesters conveniently and efficiently. A continuous flow controllable free radical polymerization platform has been developed. Through the study of polymerization reaction kinetics, 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 polyester products.

[0034] The present invention expands the characteristic scale of the microreactor from the hundred-micron level to the centimeter level by designing the internal components, and studies the strengthening effect of the internal component continuous flow reactor on the free radical polymerization process by comparing with the hundred-micron microreactor, and finds that it has a microscale effect similar to that of the hundred-micron microreactor. The reaction time is effectively shortened and the molecular weight distribution index is reduced. In addition, through the laboratory results of small-scale synthesis, the actual situation of the industrial process is reflected as comprehensively as possible, and large-scale production of poly (meth) acrylate is carried out.

[0035] The present invention shows that compared with a typical microreactor (inner diameter = 1mm), the reaction conversion rate is reduced and the polymer molecular weight distribution index is increased by using a continuous flow reactor (inner diameter>1mm). The present invention makes the macro (internal component) microreactor process strengthening effect similar to or even better than that of a typical microreactor by enlarging the reactor scale and introducing passively strengthened internal components. Further, by designing several macro-microreactors, it was found experimentally that the process strengthening effect of the spiral internal component microreactor is better than that of other internal component microreactors. At the same time, the method has the advantages of simple operation, mild conditions, effective shortening of reaction time, and reduction of polymer molecular weight distribution index.

[0036] The present invention conducts free radical polymerization based on macro-microreactors, shortens the copper-catalyzed free radical polymerization reaction time, and improves the conversion rate. In addition, the present invention expands the characteristic scale of the microreactor from hundreds of microns to centimeters by designing internal components, which can achieve high-throughput synthesis and large-scale preparation of polymers, and promote the industrial application of free radical polymerization.

[0037] The present invention provides a method for free radical polymerization based on a macro-microreactor. The provided macro-microreactor can have the microscale effect of a microreactor of 100 micrometers, expand the characteristic size of the microreactor to the centimeter level, and can synthesize poly(methyl)acrylate and its copolymers with high throughput, effectively solving the problems of continuous flow reactor (inner diameter>1mm) in the prior art, reduced reaction conversion rate, increased polymer molecular weight distribution index, and long reaction time of kettle reactor.

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

[0039] (1) The present invention is based on the macro-microreactor-enhanced copper-catalyzed free radical polymerization process to quickly and high-throughput prepare poly(meth)acrylate and its copolymers.

[0040] (2) Compared with the traditional tank reactor, the present invention significantly shortens the reaction time based on the macro-micro reactor, improves 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 of the zero-valent copper-catalyzed free radical polymerization of methyl acrylate and α-bromoisobutyrate is shortened from 100 min to 5 min, the conversion rate is increased from 47.4%-51.4% to 68.7%-75.4%, the molecular weight distribution index is reduced from 1.25-1.26 to 1.10-1.1, and the closeness between the actual number average molecular weight and the theoretical number average molecular weight in the macro-micro reactor (such as M n,theo =97266 g / mol (macro-micro reactor) vs M n,GPC = 98820 g / mol (macro-micro reactor)) is closer to the actual number average molecular weight in the kettle reactor than the theoretical number average molecular weight (such as M n,theo=61146 g / mol (kettle type) vs M n,GPC =71320g / mol (kettle type)) is closer.

[0041] (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, the flow rate is increased from 0.2 mL / min to 20 mL / min, the output per unit time is increased from 0.047 g / min to 4.3817-5.8143 g / min, and 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 the continuous flow reactor (>2.0 mm without internal components), the present invention significantly improves the conversion rate based on the macro-micro reactor, 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 conversion rate of methyl acrylate and α-bromoisobutyrate ethyl ester catalyzed by zero-valent copper is increased from 50.1% to 68.7%-75.4%, the molecular weight distribution index is reduced from 1.30 to 1.10-1.16, and the closeness between the actual number average molecular weight and the theoretical number average molecular weight in the macro-micro reactor (such as M n,theo =97461 g / mol (macro-micro reactor) vs M n,GPC =98820 g / mol (macro-micro reactor)) is closer to the actual number average molecular weight in the continuous flow reactor than the theoretical number average molecular weight (M n,theo =64629 g / mol (continuous flow) vs M n,GPC =69710 g / mol (continuous flow)) is closer. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] 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.

[0044] Figure 1 Schematic diagram of the microreactor system used in this experiment.

[0045] Figure 2 For the polymethyl acrylate of Example 1 1 H NMR spectra.

[0046] Figure 3 For Example 3 polyglycidyl methacrylate 1 H NMR spectra. DETAILED DESCRIPTION

[0047] 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.

[0048] 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 poly(meth)acrylate sample was placed in a NMR tube, deuterated chloroform was added, and the sample was measured after shaking until it was completely dissolved.

[0049] The following examples are all carried out in a macro-micro reactor system. In certain embodiments, the macro-micro reactor system is as follows Figure 1 As shown, the injection device syringe is connected to the macro-micro reactor, the macro-micro reactor is provided with a heating device, and then connected to the material receiving device. In some embodiments, the macro-micro reaction system includes a first syringe, a second syringe, a first macro-micro reactor, a second macro-micro reactor and a material receiving device, the first syringe is connected to the first macro-micro reactor in parallel, the first macro-micro reactor and the second syringe are connected to the second macro-micro reactor in parallel, and then connected to the material receiving device, and at the same time, the first macro-micro reactor and the second macro-micro reactor are both provided with a heating device.

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

[0051] Table 1

[0052]

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

[0054] Example 1

[0055] The macro-microreactor HSI (4-1-3, retention volume of 100.00 mL) was activated before each use. In a 250 mL reaction bottle filled with inert gas, 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. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 20 mL / min, that is, 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. Through 1 The conversion rate was 75.4% and the theoretical molecular weight was 97461 g / mol by H NMR. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol. This process was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polymethyl acrylate. The number average molecular weight of polymethyl acrylate was 98820 g / mol, the molecular weight distribution index was 1.10, the unit time output was 5.8143 g / min, and the NMR was as follows Figure 2 shown.

[0056] Example 2

[0057] The macro-microreactor HSI (4-1-3, with a retention volume of 50 mL) is activated before each use. 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) are added to a 100 mL reaction bottle filled with inert gas. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 1 mL / min, that is, the residence time is 50 min. The reaction temperature is 60°C, and the reaction is started. The reaction solution is collected after 100 min, and the reaction solution is quenched with liquid nitrogen. Through 1 The conversion rate measured by HNMR was 58.2%, and the theoretical molecular weight was 87300 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polymethyl methacrylate. The number average molecular weight of polymethyl methacrylate was 87610 g / mol, the molecular weight distribution index was 1.18, and the output per unit time was 0.1031 g / min.

[0058] Example 3

[0059] The macro-microreactor HSI (10-1.5-3, retention volume of 100 mL) is activated before each use. In a 250 mL reaction bottle filled with inert gas, 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) are added. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 20 mL / min, that is, the residence time is 5 min. The reaction temperature is 40°C, and the reaction is started. After 10 minutes, the reaction solution is collected and quenched with liquid nitrogen. Through 1H NMR measured the conversion rate to be 68.7% and the theoretical molecular weight to be 97657 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain poly(glycidyl methacrylate). The number average molecular weight of poly(glycidyl methacrylate) was 98760 g / mol, the molecular weight distribution index was 1.19, the unit time output was 5.4017 g / min, and the NMR was as follows Figure 3 shown.

[0060] Example 4

[0061] The macro-microreactor HSI (10-1.5-3, with a retention volume of 50 mL) was activated before each use. 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 to a 100 mL reaction bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle 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, that is, the residence time was 25 min. The reaction temperature was 50°C, and the reaction was started. The reaction solution was collected after 50 min, and the reaction solution was quenched with liquid nitrogen. By 1 The conversion rate measured by HNMR was 50.4%, and the theoretical molecular weight was 86291 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polyethyl methacrylate. The number average molecular weight of polyethyl methacrylate is 90870 g / mol, the molecular weight distribution index is 1.26, and the output per unit time is 0.2780 g / min.

[0062] Example 5

[0063] The macro-microreactor HSI (5-1.5-3, with a retention volume of 25 mL) was activated before each use. 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 to a 100 mL reaction bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 5 mL / min, that is, the residence time was 5 min. The reaction temperature was 20 ° C, and the reaction was started. After 10 minutes, the reaction solution was collected and quenched with liquid nitrogen. Through 1 The conversion rate measured by H NMR was 53.8%, and the theoretical molecular weight was 80700 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polyethyl acrylate. The number average molecular weight of polyethyl acrylate was 82780 g / mol, the molecular weight distribution index was 1.24, and the output per unit time was 0.7451 g / min.

[0064] Example 6

[0065] The macro-microreactor HSI (10-3-10, with a retention volume of 50 mL) is activated before each use. In a 100 mL reaction bottle filled with inert gas, 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) are added. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 1 mL / min, that is, the residence time is 50 min. The reaction temperature is 30°C, and the reaction is started. The reaction solution is collected after 100 min, and the reaction solution is quenched with liquid nitrogen. Through 1HNMR measured a conversion rate of 32.4%. The reaction solution was stored in a vial for acetylation. To remove the residual solvent more quickly, the polymer sample stored in the vial was dissolved in pyridine (0.5 mL pyridine / 20 mg polymer), and then acetic anhydride (0.1 mL) was added. The polymer was then precipitated in methanol. The centrifuge was centrifuged and rinsed with MeOH several times, the polymer precipitate was collected, dried and dissolved in tetrahydrofuran and used for GPC analysis (relative to PMMA standard). The reaction solution was precipitated by adding cold methanol solution, the product was collected by centrifugation, and after the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, repeated three times, and the product was fully washed. The cleaned product was placed in a vacuum drying oven and dried at 35 ° C for 48 hours to obtain poly(hydroxyethyl methacrylate). The number average molecular weight of poly(hydroxyethyl methacrylate) is 70190 g / mol, the molecular weight distribution index is 1.28, and the unit time output is 0.0897 g / min.

[0066] Example 7

[0067] The macro-microreactor HSI (2-0.5-1, with a retention volume of 5 mL) was activated before each use. 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 aqueous methanol solution (40% H2O in MeOH) were added to a 100 mL reaction bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 1 mL / min, that is, the residence time was 5 min. The reaction temperature was 30°C, and the reaction was started. The reaction solution was collected after 10 min, and the reaction solution was quenched with liquid nitrogen. By 1 H NMR measured a conversion rate of 43.4%. The residue was stored in a vial for acetylation. The residual solvent was removed more quickly, and the polymer sample stored in the vial was dissolved in pyridine (0.5 mL pyridine / 20 mg polymer), and then acetic anhydride (0.1 mL) was added. The polymer was then precipitated in methanol. The centrifuge was centrifuged and rinsed with MeOH several times, the polymer precipitate was collected, dried and dissolved in tetrahydrofuran and used for GPC analysis (relative to PMMA standard). The reaction solution was precipitated by adding cold methanol solution, the product was collected by centrifugation, and after the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, repeated three times, and the product was fully washed. The cleaned product was placed in a vacuum drying oven and dried at 35 ° C for 48 hours to obtain polyhydroxyethyl acrylate. The number average molecular weight of polyhydroxyethyl acrylate is 60160 g / mol, the molecular weight distribution index is 1.28, and the unit time output is 0.1544 g / min.

[0068] Example 8

[0069] The macro-microreactor HSI (3-1-10, with a retention volume of 50 mL) was activated before each use. In a 250 mL reaction bottle filled with inert gas, 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. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 5 mL / min, that is, 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. Through 1 The conversion rate measured by H NMR was 54.0%, and the theoretical molecular weight was 46440 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polymethyl acrylate. The number average molecular weight of polymethyl acrylate was 45680 g / mol, the molecular weight distribution index was 1.27, and the output per unit time was 1.4571 g / min.

[0070] Example 9

[0071] The macro-microreactor HSI (10-3-5, retention volume of 50 mL) was activated before each use. 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 tris(2,2,2-trifluoroethyl) phosphate aqueous solution (10% H2O in TFP) were added to a 250 mL reaction bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 10 mL / min, that is, the residence time was 5 min. The reaction temperature was 50 ° C, and the reaction was started. After 10 minutes, the reaction solution was collected and quenched with liquid nitrogen. By 1The conversion rate measured by H NMR was 49.3%, and the theoretical molecular weight was 70006 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 1.3091 g / min.

[0072] Example 10

[0073] The macro-microreactor HSI (4-1-3, with a retention volume of 100 mL) is activated before each use. In a 250 mL reaction bottle filled with inert gas, 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) are added. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 20 mL / min, that is, the residence time is 5 min. The reaction temperature is 30°C, and the reaction is started. After 10 minutes, the reaction solution is collected and quenched with liquid nitrogen. Through 1 The conversion rate measured by H NMR was 55.4%, and the theoretical molecular weight was 95288 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polymethyl acrylate. The number average molecular weight of polymethyl acrylate was 95680 g / mol, the molecular weight distribution index was 1.17, and the output per unit time was 3.9814 g / min.

[0074] Embodiment 11

[0075] The macro-microreactor HSI (4-1-3, with a retention volume of 100 mL) is activated before each use. In a 250 mL reaction bottle filled with inert gas, 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) are added. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 20 mL / min, that is, the residence time is 5 min. The reaction temperature is 30°C, and the reaction is started. After 10 minutes, the reaction solution is collected and quenched with liquid nitrogen. Through 1 The conversion rate measured by H NMR was 41.9%, and the theoretical molecular weight was 90085 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 2.9301 g / min.

[0076] Example 12

[0077] The macro-microreactor HSI (4-1-3, with a retention volume of 100 mL) is activated before each use. In a 250 mL reaction bottle filled with inert gas, 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) are added. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 20 mL / min, that is, the residence time is 5 min. The reaction temperature is 30°C, and the reaction is started. After 10 minutes, the reaction solution is collected and quenched with liquid nitrogen. Through 1The conversion rate measured by H NMR was 41.3%, and the theoretical molecular weight was 79401 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polybutyl acrylate. The number average molecular weight of polybutyl acrylate was 81540 g / mol, the molecular weight distribution index was 1.17, and the output per unit time was 2.8971 g / min.

[0078] Embodiment 13

[0079] The macro-microreactor HSI (4-1-3, with a retention volume of 100 mL) is activated before each use. In a 250 mL reaction bottle filled with inert gas, 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) are added. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 20 mL / min, that is, the residence time is 5 min. The reaction temperature is 30°C, and the reaction is started. After 10 minutes, the reaction solution is collected and quenched with liquid nitrogen. Through 1 The conversion rate measured by H NMR was 44.7%, and the theoretical molecular weight was 85938 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polytert-butyl acrylate. The number average molecular weight of polytert-butyl acrylate was 87540 g / mol, the molecular weight distribution index was 1.18, and the output per unit time was 3.0973 g / min.

[0080] Embodiment 14

[0081] The reactors for both reactions were macro-microreactors HSI (4-1-3, with a retention volume of 5 mL), and the macro-microreactors were 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 bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the 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, that is, the residence time was 100 min. The reaction temperature was 30°C, and the reaction was started. The reaction solution was collected after 200 min, and the reaction solution was quenched with liquid nitrogen. By 1 The conversion rate was measured by H NMR and was 92.7%. The number average molecular weight of poly(glycidyl methacrylate) was 197701 g / mol, and the molecular weight distribution index was 1.20. Then, 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 time, the total flow rate in the second stage reaction tube was 0.1 mL / min, and the retention time was 50 min. After 100 min of reaction, a poly(glycidyl methacrylate)-block-poly(methyl methacrylate) reaction solution was obtained. 1 The conversion rate measured by HNMR was 52.7%. The number average molecular weight of poly(glycidyl methacrylate)-block-poly(methyl methacrylate) was 257540 g / mol, and the molecular weight distribution index was 1.28.

[0082] Embodiment 15

[0083] The macro-microreactor HSI (10-3-5, retention volume of 50 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 bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 20 mL / min, that is, the residence time was 2.5 min. The reaction temperature was 30°C, and the reaction was started. The reaction solution was collected after 5 min, and the reaction solution was quenched with liquid nitrogen. Through 1The conversion rate measured by H NMR was 50.3%, and the theoretical molecular weight was 65082 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 3.5013 g / min.

[0084] Example 16

[0085] The macro-microreactor SLSI (4-2, retention volume of 100 mL) was activated before each use. In a 250 mL reaction bottle filled with inert gas, 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. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 20 mL / min, that is, 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. Through 1 The conversion rate measured by H NMR was 65.4%, and the theoretical molecular weight was 84561 g / mol. The reaction solution was added with cold methanol solution for precipitation, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and the precipitation was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 4.7088 g / min.

[0086] Embodiment 17

[0087] The macro-microreactor SSI (D-1, 4-2-3, with a retention volume of 100 mL) was activated before each use. In a 250 mL reaction bottle filled with inert gas, 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. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 20 mL / min, that is, 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. By 1 The conversion rate measured by H NMR was 71.1%, 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 the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and the precipitation was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 4.9172 g / min.

[0088] Embodiment 18

[0089] The macro-microreactor SSI (D-2, 4-2-3, with a retention volume of 100 mL) was activated before each use. In a 250 mL reaction bottle filled with inert gas, 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. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 20 mL / min, that is, 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. By 1The conversion rate measured by H NMR was 71.3%, 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 the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and the precipitation was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 5.1348 g / min.

[0090] Embodiment 19

[0091] The macro-microreactor OSI (4-2-3, with a retention volume of 100 mL) was activated before each use. In a 250 mL reaction bottle filled with inert gas, 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. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 20 mL / min, that is, 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. By 1 The conversion rate measured by H NMR was 68.7%, and the theoretical molecular weight was 88818 g / mol. The reaction solution was added with cold methanol solution for precipitation, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and the precipitation was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 4.3817 g / min.

[0092] Embodiment 20

[0093] The macro-microreactor HSI (4-1-3, with a retention volume of 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 bottle filled with inert gas. After the addition was completed, the reaction solution was deoxygenated. The solution in the reaction bottle was transferred into the syringe of the injection device, and the syringe pump was connected to the continuous flow system. The flow rate was set to 0.2 mL / min, that is, the residence time was 25 min. The reaction temperature was 30°C, and the reaction was started. The reaction solution was collected after 50 min, and the reaction solution was quenched with liquid nitrogen. Through 1 The conversion rate measured by H NMR was 60.4%, and the theoretical molecular weight was 77970 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polymethyl acrylate. The number average molecular weight of polymethyl acrylate was 79820 g / mol, the molecular weight distribution index was 1.17, and the output per unit time was 0.043 g / min.

[0094] Comparative Example 1

[0095] Place a typical microreactor (copper tube with inner diameter = 1 mm and retention volume of 5.00 mL) and activate the continuous flow microreactor before each use. Add 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) to a 100 mL reaction bottle filled with inert gas. After the addition is completed, deoxygenate the reaction solution. Transfer the solution in the reaction bottle into the syringe of the injection device, and connect it to the injection pump and the continuous flow system. Set the flow rate to 0.2 mL / min, that is, the residence time is 25 min. The reaction temperature is 30°C, start the reaction, collect the reaction solution after 50 minutes, and quench the reaction solution with liquid nitrogen. Through 1The conversion rate measured by H NMR was 63.8%, and the theoretical molecular weight was 82497 g / mol. The reaction solution was added with cold methanol solution for precipitation, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and the precipitation was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours to obtain polymethyl acrylate, the number average molecular weight of polymethyl acrylate was 87490 g / mol, the molecular weight distribution index was 1.18, and the output per unit time was 0.047 g / min.

[0096] Comparative Example 2

[0097] In a typical microreactor (copper tube with inner diameter = 1mm and retention volume of 100.00mL), the continuous flow microreactor is activated before each use. 90.363g (1050mmol) of MA, 0.1365g (0.7mmol) of EBiB, 0.0403g (0.175mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), and 135.8097g (W = 40%) of dimethyl sulfoxide (DMSO) are added to a 250mL reaction bottle filled with inert gas. After the addition is completed, the reaction solution is deoxygenated. The solution in the reaction bottle is transferred into the syringe of the injection device, and the syringe pump is connected to the continuous flow system. The flow rate is set to 20mL / min, that is, the residence time is 5min. The reaction temperature is 30°C, the reaction is started, and the reaction solution is collected after 10min, and the reaction solution is quenched with liquid nitrogen. During the reaction, the instrument alarms and the reaction solution does not flow out.

[0098] Comparative Example 3

[0099] Place the continuous microreactor (copper tube with inner diameter = 4 mm and retention volume of 100.00 mL), and activate the continuous flow microreactor before each use. Add 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) to a 250 mL reaction bottle filled with inert gas. After the addition is completed, the reaction solution is deoxygenated. Transfer the solution in the reaction bottle into the syringe of the injection device, and connect it to the injection pump and the continuous flow system. Set the flow rate to 20 mL / min, that is, the residence time is 5 min. The reaction temperature is 30°C, start the reaction, collect the reaction solution after 10 minutes, and quench the reaction solution with liquid nitrogen. Through 1The conversion rate measured by H NMR was 50.1%, and the theoretical molecular weight was 64824 g / mol. The reaction solution was added with cold methanol solution for precipitation, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and the precipitation was repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 3.6172 g / min.

[0100] Comparative Example 4

[0101] In a 100mL reaction bottle filled with inert gas, add 25.818g (300mmol) of MA, 0.0390g (0.2mmol) of EBiB, 0.0115g (0.05mmol) of tris(2-dimethylaminoethyl)amine (Me6-TREN), 40mg of copper powder (after activation), and 38.8028g (W=40%) of dimethyl sulfoxide (DMSO). After the addition is completed, the reaction solution is deoxygenated. The reaction time is 100min. The reaction temperature is 30°C. After 100min of reaction, the reaction solution is quenched with liquid nitrogen. 1 The conversion rate measured by H NMR was 51.4%, and the theoretical molecular weight was 66306 g / mol. The reaction solution was precipitated by adding cold methanol solution, and the product was collected by centrifugation. After the product was dissolved in dichloromethane, it was precipitated and centrifuged again with cold methanol, and repeated three times to fully wash the product. The washed product was placed in a vacuum drying oven and dried at 35°C for 48 hours 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 output per unit time was 0.0107 g / min.

[0102] Comparative Example 5

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

[0104] 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. Application of a macro-microreactor in the preparation of polymethacrylate and its copolymer, characterized in that: In a macro-micro reactor, methacrylate monomers, initiators, ligands and solvents are reacted to obtain polymethacrylate and copolymers thereof.

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

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

4. The use according to claim 1 or the method according to claim 2, characterized in that: The methacrylate monomer includes n-butyl methacrylate; preferably, the initiator includes p-toluenesulfonyl chloride, methyl 2-chloropropionate, 2,2-dichloroacetophenone, ethyl 2-chloropropionate, and 2-chloropropionamide; preferably, the solvent includes tris(2,2,2-trifluoroethyl) phosphate; preferably, the solvent is any one or a combination of tris(2,2,2-trifluoroethyl) phosphate, dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, and N,N-dimethylformamide, or a mixed solvent of any one of the foregoing and water, and the water content in the mixed solvent is 10-40% vt.

5. The use according to claim 1 or the method according to claim 1, characterized in that: The reaction temperature is 20-60°C, preferably 20-40°C, and more preferably 30°C; the solid content of the reaction is 20-60%, preferably 30-50%, and more preferably 40%; Preferably, the molar ratio of the monomer to the initiator is 100-2500:1, preferably 1000-2500:1, and more preferably 1500:

1.

6. The use according to claim 1 or the method according to claim 2, characterized in that: The molar ratio of the monomer to the ligand is 4000-10000:1, preferably 6000:1; preferably, the flow rate of the reaction is 1-20 mL / min, preferably 5-20 mL / min, preferably 10-20 mL / min; preferably, the reaction retention time is 2.5-50 min, preferably 2.5-25 min; the flow rate of the reaction is 0.05-20 mL / min.

7. The use according to claim 1 or the method according to claim 2, characterized in that: The macro-microreactor comprises a channel shell and an internal component in the channel shell; the internal component is a spiral internal component, a serpentine internal component, a linear internal component or an O-shaped internal component; the internal component is a copper internal component; the inner diameter of the channel shell is 2-10 mm, the diameter of the internal component is 0.5-3 mm, and the pitch of the spiral internal component, the serpentine internal component, and the O-shaped internal component are independently selected from 1-10 mm.

8. The use according to claim 1 or the method according to claim 1, characterized in that: The flow rate of the reaction is 0.2-20 mL / min; preferably, the retention time of the reaction is 2.5-100 min.

9. The use according to claim 1 or the method according to claim 2, characterized in that: The macro-micro reactor comprises a channel shell and a spiral internal component in the channel; the spiral internal component in the channel is made of copper.

10. A method for preparing polyacrylate and its copolymer based on macro-micro reactor, characterized in that: In a macro-microreactor, an acrylate monomer is reacted with an initiator, a ligand and a solvent to obtain polymethacrylate and a copolymer thereof; preferably, the acrylate monomer is any one or a combination of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate and tert-butyl acrylate, preferably methyl acrylate; Preferably, the initiator is any one or a combination of ethyl α-bromoisobutyrate, methyl α-bromophenylacetate, ethyl α-bromophenylacetate, methyl 2-bromopropionate, ethyl 2-bromopropionate, p-toluenesulfonyl chloride, methyl 2-chloropropionate, 2,2-dichloroacetophenone, ethyl 2-chloropropionate, and 2-chloropropionamide, preferably ethyl α-bromoisobutyrate; Preferably, the ligand is any one of tris[2-(dimethylamino)ethyl]amine, pentamethyldiethylenetriamine, tris(2-pyridylmethyl)amine, preferably tris[2-(dimethylamino)ethyl]amine; Preferably, the solvent is any one or a combination of dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, N,N-dimethylformamide, tris(2,2,2-trifluoroethyl) phosphate, or any one or a combination of tris(2,2,2-trifluoroethyl) phosphate, dimethyl sulfoxide, 2,2,2-trifluoroethanol, isopropanol, methanol, acetonitrile, N,N-dimethylformamide, or a mixed solvent of any one of the foregoing and water, wherein the water content in the mixed solvent is 5-45% vt, preferably dimethyl sulfoxide; Preferably, 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, and more preferably 6000:1; the solid content of the reaction is 20-60%, preferably 30-50%, and more preferably 40%; Preferably, the reaction temperature is 20-60°C, preferably 20-40°C, and more preferably 30°C; Preferably, 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; Preferably, the macro-microreactor comprises a channel shell and an internal component in the channel shell; the internal component is a spiral internal component, a serpentine internal component, a linear internal component or an O-shaped internal component; the internal component is a copper internal component; The inner diameter of the channel housing is 2-10 mm, the diameter of the inner member is 0.5-3 mm, and the pitches of the spiral inner member, the serpentine inner member, and the O-shaped inner member are independently selected from 1-10 mm.

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