CN114539453A - Coupling photocatalysis controllable cationic polymerization method - Google Patents
Coupling photocatalysis controllable cationic polymerization method Download PDFInfo
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- 238000010538 cationic polymerization reaction Methods 0.000 title claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 17
- 230000008878 coupling Effects 0.000 title claims abstract description 8
- 238000010168 coupling process Methods 0.000 title claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 8
- 238000007146 photocatalysis Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- 239000000178 monomer Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 238000005286 illumination Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000010791 quenching Methods 0.000 claims abstract description 14
- 230000000171 quenching effect Effects 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000005086 pumping Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 99
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 34
- 239000010453 quartz Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000011324 bead Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical group COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 17
- -1 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate Chemical group 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
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- 238000007605 air drying Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 abstract description 17
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 30
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- 239000007924 injection Substances 0.000 description 29
- 238000009826 distribution Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
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- 238000001542 size-exclusion chromatography Methods 0.000 description 16
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- 238000006116 polymerization reaction Methods 0.000 description 6
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- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F112/22—Oxygen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for coupling photocatalytic controllable cationic polymerization, which comprises the following steps: (1) dissolving a monomer in an organic solvent under the condition of anhydrous inert gas atmosphere to obtain a mixed system for later use; (2) dissolving alcohol and a photocatalyst in an organic solvent under the atmosphere of anhydrous inert gas to obtain a mixed system for later use; (3) in a microchannel reaction device, pumping the two mixed systems prepared in the steps (1) and (2) into a microreactor provided with a light source and a transparent sphere internal member simultaneously, reacting under the illumination condition, and collecting reaction liquid; (4) and (4) adding a quenching agent and an organic solvent into the reaction liquid collected in the step (3) in sequence, and separating and purifying to obtain a final product. The invention utilizes a microreactor system containing internals to combine with the cationic polymerization of photocatalysis, greatly improves the mixing efficiency, shortens the reaction time, realizes continuous production, and has the advantages of greenness, safety, high efficiency, high reaction rate, mild reaction conditions and the like.
Description
Technical Field
The invention belongs to the technical field of controllable cationic polymerization, and particularly relates to a coupling photocatalysis controllable cationic polymerization method.
Background
Compared to conventional batch reactors, microreactors have a large specific surface area, which is advantageous in organic chemistry and polymer synthesis, and their large surface-to-volume ratio and continuous flow characteristics allow improved momentum/mass/heat transfer and high level of control of the reaction process. The use of continuous flow techniques has been shown to accelerate the polymerization rate, achieve narrower dispersion and higher chemical selectivity under different polymerization regimes.
However, the conventional microreactor is characterized in that the fluid passes through a tube with a reynolds number of less than 2000 due to the effect of laminar flow, and the laminar flow results in a parabolic velocity distribution, so that the reaction solution undergoes different retention times due to the friction between the interface of the mobile phase and the fixed tube, thereby having a certain side effect on the polymer synthesis.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention provides a method for coupling photocatalytic controllable cationic polymerization, which strengthens the mass and heat transfer process of the prior micro-reaction technology to improve the controllability of the reaction.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a method for coupling photocatalytic controllable cationic polymerization comprises the following steps:
(1) dissolving vinyl monomers in an organic solvent under the condition of anhydrous inert gas atmosphere to obtain a mixed system for later use;
(2) dissolving alcohol and a photocatalyst in an organic solvent under the atmosphere of anhydrous inert gas to obtain a mixed system for later use;
(3) in a microchannel reaction device, pumping the two mixed systems prepared in the steps (1) and (2) into a microreactor provided with a light source and a transparent sphere internal member simultaneously, reacting under the illumination condition, and collecting reaction liquid;
(4) and (4) adding a quenching agent and an organic solvent into the reaction liquid collected in the step (3) in sequence, and separating and purifying to obtain a final product.
Preferably, in the step (1), the vinyl monomer is 4-methoxystyrene; the organic solvent is one or more of dichloromethane and dichloroethane.
Preferably, in the step (2), the alcohol is one or more of methanol, ethanol, isopropanol, tert-butanol and trifluoroethanol; the photocatalyst is 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate; the organic solvent is one or more of dichloromethane and dichloroethane.
Preferably, in the step (3), the molar ratio of the vinyl monomer to the alcohol is 10-400: 1; the using amount of the alcohol is 3.3 to 26 percent of the using amount of the vinyl monomer in terms of mole percentage; in the mixed system obtained in the step (1), the concentration of the vinyl monomer is 0.3-3 mol/L.
Preferably, in the step (3), the reaction flow rate of the reaction is 0.1-0.8 mL/min; the reaction residence time is 3-120 min, the reaction retention volume is 2-25 mL, and the reaction temperature is normal temperature; the illumination wavelength of the light source is 400-500 nm.
Preferably, in the step (3), the material of the microreactor reaction channel is a high-permeability PFA material or a quartz tube, the inner diameter of the channel is 1-10 mm, and the length of the channel is 90-760 mm; the diameter of the internal components of the transparent sphere is 1.0-6.0mm, and the internal components of the sphere are randomly and alternately distributed in the micro-reactor channel; the transparent spherical inner member is quartz beads or glass beads, preferably quartz beads.
Preferably, in the step (3), the microchannel reaction device further includes a first feeding pump, a second feeding pump, a micro mixer and a receiver, the first feeding pump and the second feeding pump are arranged in parallel and are connected to the micro mixer at the same time, the micro mixer, the microreactor and the receiver are sequentially arranged in series, the light source is arranged outside the microreactor pipeline, and the first feeding pump, the second feeding pump and the micro mixer are all used for shading.
Preferably, in the step (4), the quenching agent is triethylamine, and the amount of the quenching agent is 1-5 times of the molar amount of the photocatalyst in the collected reaction liquid; the organic solvent is selected from one or two of methanol or n-hexane, and the amount of the organic solvent is 20-100 times of the volume of the collected reaction liquid.
Preferably, in the step (4), the separation and purification method comprises: placing in a refrigerator at-20 deg.C for 15-25min, centrifuging, filtering for several times, air drying the obtained precipitate, and vacuum drying
By adding the transparent spherical internal member, the invention can improve the internal fluid state of the micro-reaction pipeline, reduce the Poiseuille fluid effect, form the disturbance effect, enhance the mixing and mass and heat transfer efficiency of the micro-reactor, improve the polymerization rate, and ensure that the molecular weight of the obtained polymer is closer to the theoretical value and the molecular weight distribution index is narrower. Meanwhile, the size of the reaction tube can be increased, such as centimeter level, the flux of a micro-reaction system is increased, and the method has important significance for industrialization of continuous flow technology.
The invention combines the micro-flow field technology with the photocatalysis controllable cationic polymerization system, constructs a micro-reaction unit aiming at specific photocatalyst and corresponding monomer, and realizes the promotion of polymerization reaction rate and the optimization of molecular weight distribution index; the fluid in the pipeline is disturbed by the aid of the inner member, mass transfer and heat transfer efficiency of the micro-flow field technology is enhanced, accurate space-time positioning of the cationic monomer is carried out, the structure of the homopolymer is accurately constructed, and the homopolymer with the controllable structure and chain length is finally obtained. The method provides a new technical reference for controllable cationic polymerization under continuous flow, and simultaneously provides a good reference for light-mediated polymerization in a microreactor.
Has the advantages that: compared with the traditional kettle type reactor and the traditional microreactor, the novel method for coupling the microreactor with the internal component to control the cationic polymerization breaks through plug flow, enhances the excellent mixing, mass and heat transfer efficiency and reaction process of the microreactor, improves the polymerization reaction rate, shortens the reaction time, obtains the polymer with narrower molecular weight distribution index, can better control the reaction condition, and is expected to be applied to industrial production.
Drawings
FIG. 1 is a schematic view of a microchannel module reactor and an inner member micro-reaction channel, which includes: sample feeding devices 1 and 2, a micro mixer 3, an illumination device 4 and a product collector 5.
FIG. 2 is a GPC chart of the resulting polymer, polymethoxystyrene (PMP) of example 1, having a number average molecular weight of 5100g/moL and a molecular weight distribution index of 1.10.
FIG. 3 shows PMP of example 11H NMR chart.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
In the following examples of the present invention, the molecular weight and molecular weight distribution index of the product were measured by the following methods.
Using a Wyatt size exclusion chromatography system, a GPC column equipped with an SSI 1500 pump, a Wyatt OptilabEX detector, Waters Styragel HR;
analysis conditions were as follows: the mobile phase is tetrahydrofuran, the flow rate is 0.7mL/min, the column temperature is 35 ℃, and the injection volume is 0.4 mL.
Sample measurement: taking 4mg of a pure sample, adding 1mL of tetrahydrofuran solution into a centrifuge tube for dilution, filtering by using a disposable filter head (containing a 0.33um organic filter membrane), and taking 4mL of solution for sample measurement.
In the following examples of the present invention, the conversion C represents the molar ratio of the reacted monomers to the total amount of the starting monomers and can be calculated as follows:
C＝(na/n0)*100％
wherein C represents the conversion of the monomer, naDenotes the molar amount of monomer reacted, n0Representing the total molar amount of the initial monomers.
The adopted microchannel reaction device comprises a first feeding pump (material feeding device 1), a second feeding pump (material feeding device 1), a micro mixer 3, a micro reactor and a receiver (product collector 5), wherein the first feeding pump and the second feeding pump are arranged in parallel and are simultaneously connected to the micro mixer 3, the micro reactor and the receiver are sequentially arranged in series, an illumination device 4 is arranged outside a micro reactor pipeline, and the first feeding pump, the second feeding pump and the micro mixer 3 are all subjected to shading treatment. The components in the quartz bead ball bodies are randomly and alternately distributed in the micro-reactor pipeline.
Example 1
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a pipeline as a quartz tube with the inner diameter of 2mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the illumination wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding a quenching agent of 0.2mL triethylamine and 80mL methanol, placing in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 5100g/mol, the molecular weight distribution index is 1.10, and the conversion rate is 99%.
Example 2
Respectively adding 4-methoxystyrene (4.04g, 30mmol), dichloromethane (12.6mL), 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), and dichloromethane (12.6mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, mixing uniformly, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, controlling the inner diameter to be 3mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 6mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the illumination wavelength to be 450nm, collecting 2mL after the reaction is stabilized for 10min, sequentially adding 0.2mL triethylamine and 80mL methanol as quenchers, placing in a refrigerator for 20min at-20 ℃, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 12100g/mol, the molecular weight distribution index is 1.24, and the conversion rate is 97%.
Example 3
Respectively adding 4-methoxystyrene (10.1g, 75mmol), dichloromethane (25.2mL), 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), and dichloromethane (25.2mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, mixing uniformly, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, adjusting the inner diameter to be 8mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 9mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the illumination wavelength to be 450nm, collecting 2mL after 15min reaction is stable, sequentially adding 0.2mL triethylamine and 80mL methanol as quenchers, placing in a refrigerator for 20min at-20 ℃, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 25400g/mol, the molecular weight distribution index is 1.26, and the conversion rate is 97%.
Example 4
Respectively adding 4-methoxystyrene (20.2g, 150mmol), dichloromethane (25.2mL), and pyridinium 2,4, 6-tri (p-tolyl) tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), and dichloromethane (25.2mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, mixing uniformly, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, adjusting the inner diameter to be 10mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 15mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the illumination wavelength to be 450nm, collecting 2mL after the reaction is stabilized for 25min, sequentially adding 0.2mL triethylamine and 80mL methanol as quenchers, placing in a refrigerator for 20min at-20 ℃, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 52400g/mol, the molecular weight distribution index is 1.29, and the conversion rate is 96%.
Example 5
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, controlling the inner diameter to be 2mm, selecting quartz beads with the diameter of 1.5mm as internal components, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the light wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding 0.2mL triethylamine and 80mL methanol as quenchers, placing in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 4900g/mol, the molecular weight distribution index is 1.15, and the conversion rate is 94%.
Example 6
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL), 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous and anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, controlling the inner diameter to be 3mm and the reserved volume to be 6mL, selecting and adding inner members to be quartz beads with the diameter of 1mm, controlling the reaction temperature of the reactor to be 25 ℃, turning on a light source to start reaction, controlling the illumination wavelength to be 450nm, collecting 2mL after the reaction is stabilized for 10min, adding a quenching agent of 0.2mL triethylamine and 80mL of methanol in sequence, placing the reaction bottle in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 4900g/mol, the molecular weight distribution index is 1.18, and the conversion rate is 92%.
Example 7
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL), 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous and anaerobic treatment, shaking, mixing uniformly, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube with an inner diameter of 3mm, selecting quartz beads with the diameter of 2mm as internal components, keeping the volume to be 4mL, starting reaction at the reaction temperature of the reactor of 25 ℃, turning on a light source to react, collecting 2mL after the reaction is stabilized at 7min, adding a quenching agent of 0.2mL triethylamine and 80mL methanol, placing in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 5300g/mol, the molecular weight distribution index is 1.20, and the conversion rate is 90%.
Example 8
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous and anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.4mL/min, selecting a pipeline as a quartz tube with an inner diameter of 2mm, selecting an added inner member as treated quartz beads with the diameter of 1mm, keeping the volume to be 6mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the light wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding 0.2mL triethylamine and 80mL methanol as a quenching agent, placing the mixture in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 5200g/mol, the molecular weight distribution index is 1.06, and the conversion rate is 100%.
Example 9
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (16mg, 0.5mmol, 3.3 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous and anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube with the inner diameter of 2mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the light wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding triethylamine and 80mL methanol as a quenching agent, placing the mixture in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 4700g/mol, the molecular weight distribution index is 1.26, and the conversion rate is 86%.
Example 10
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), ethanol (46mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous and anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, controlling the inner diameter to be 2mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the illumination wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding 0.2mL triethylamine and 80mL methanol as quenchers, placing in a refrigerator for 20min at-20 ℃, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 5900g/mol, the molecular weight distribution index is 1.29, and the conversion rate is 88%.
Example 11
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), isopropanol (60mg, 1mmol, 6.5 mol%), and dichloromethane (12.6mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, mixing uniformly, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, controlling the inner diameter to be 2mm, selecting quartz beads with the diameter of 1mm as internal components, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the light irradiation wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding 0.2mL triethylamine and 80mL methanol as a quenching agent, placing the mixture in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 6900g/mol, the molecular weight distribution index is 1.33, and the conversion rate is 97%.
Example 12
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL), 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), tert-butyl alcohol (74mg, 1mmol, 6.5 mol%), and dichloromethane (12.6mL) into two reaction bottles after anhydrous and anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube as a pipeline, controlling the inner diameter to be 2mm, selecting and adding quartz beads with the diameter of 1mm as inner members, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the light irradiation wavelength to be 450nm, collecting 2mL after 7min reaction is stable, sequentially adding 0.2mL of a quenching agent and 80mL of methanol, placing in a refrigerator at-20 ℃ for 20min, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 5100g/mol, the molecular weight distribution index is 1.32, and the conversion rate is 97%.
Example 13
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (16.7mg, 0.19mmol, 1.25 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, uniformly mixing, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a pipeline as a quartz tube with an inner diameter of 2mm, selecting half of an added inner component as quartz beads with the diameter of 1mm, keeping the volume to be 4mL, controlling the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, controlling the light irradiation wavelength to be 450nm, collecting 2mL after the reaction is stabilized for 7min, sequentially adding 0.1mL triethylamine and 80mL methanol as quenchers, placing in a refrigerator for 20min at-20 ℃, the centrifugal filtration is circulated for 3 times, and the obtained white precipitate is air-dried and then placed in a vacuum drying oven for 48 hours. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 4100g/mol, the molecular weight distribution index is 1.18, and the conversion rate is 72%.
Comparative example 1
To the two reaction flasks after the anhydrous anaerobic treatment were added 4-methoxystyrene (2.02g, 15mmol), dichloromethane (25.2mL) and pyridinium 2,4, 6-tris (p-tolyl) tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%) in this order, and the mixture was stirred and mixed. The reaction temperature is 25 ℃, a light source is turned on to start the reaction, the illumination wavelength is 450nm, 2mL of reaction liquid is collected after 20min of reaction stabilization, 0.2mL of triethylamine and 80mL of methanol as quenchers are added in sequence, the mixture is placed in a refrigerator at the temperature of minus 20 ℃ for 20min, the centrifugal filtration cycle is carried out for 3 times, and the obtained white precipitate is placed in a vacuum drying oven for 48h after being dried in the air. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 6100g/mol, the molecular weight distribution index is 1.36, and the conversion rate is 96%.
Comparative example 2
Respectively adding 4-methoxystyrene (2.02g, 15mmol), dichloromethane (12.6mL) and 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate (33.4mg, 0.38mmol, 2.5 mol%), methanol (32mg, 1mmol, 6.5 mol%), dichloromethane (12.6mL) into two reaction bottles after anhydrous anaerobic treatment, shaking, mixing uniformly, transferring into a first material sample injection device 1 and a second material sample injection device 2, regulating the flow rate of 1 and 2 to be 0.3mL/min, selecting a quartz tube (without an internal member), setting the inner diameter to be 1mm, keeping the volume to be 6mL, setting the reaction temperature of a reactor to be 25 ℃, turning on a light source to start reaction, setting the illumination wavelength to be 450nm, collecting 2mL after 10min reaction is stable, adding a quencher of 0.2mL triethylamine and 80mL methanol, placing the mixture into a refrigerator at-20 ℃, performing centrifugal filtration for 3 times, the obtained white precipitate was air-dried and placed in a vacuum oven for 48 h. Through size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis, the PMP number average molecular weight of the obtained polymer product is 5700g/mol, the molecular weight distribution index is 1.22, and the conversion rate is 94%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A method for coupling photocatalytic controllable cationic polymerization is characterized by comprising the following steps:
(1) dissolving vinyl monomers in an organic solvent under the condition of anhydrous inert gas atmosphere to obtain a mixed system for later use;
(2) dissolving alcohol and a photocatalyst in an organic solvent under the atmosphere of anhydrous inert gas to obtain a mixed system for later use;
(3) in a microchannel reaction device, pumping the two mixed systems prepared in the steps (1) and (2) into a microreactor provided with a light source and a transparent sphere internal member simultaneously, reacting under the illumination condition, and collecting reaction liquid;
(4) and (4) adding a quenching agent and an organic solvent into the reaction liquid collected in the step (3) in sequence, and separating and purifying to obtain a final product.
2. The method for coupled photo-catalytic controlled cationic polymerization according to claim 1, wherein in the step (1), the vinyl monomer is 4-methoxystyrene; the organic solvent is one or more of dichloromethane and dichloroethane.
3. The coupled photocatalytic controllable cationic polymerization method according to claim 1, wherein in the step (2), the alcohol is one or more of methanol, ethanol, isopropanol, tert-butanol and trifluoroethanol; the photocatalyst is 2,4, 6-tri (p-tolyl) pyridinium tetrafluoroborate; the organic solvent is one or more of dichloromethane and dichloroethane.
4. The method for coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in the step (3), the molar ratio of the vinyl monomer to the alcohol is 10-400: 1; the using amount of the alcohol is 3.3 to 26 percent of the using amount of the vinyl monomer in terms of mole percentage; in the mixed system obtained in the step (1), the concentration of the vinyl monomer is 0.3-3 mol/L.
5. The method for coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in the step (3), the reaction flow rate of the reaction is 0.1-0.8 mL/min; the reaction residence time is 3-120 min, the reaction retention volume is 2-25 mL, and the reaction temperature is normal temperature; the illumination wavelength of the light source is 400-500 nm.
6. The coupled photocatalytic controllable cationic polymerization method according to claim 1, wherein in the step (3), the material of the microreactor reaction channel is a high-permeability PFA material or a quartz tube, the inner diameter of the channel is 1-10 mm, and the length of the channel is 90-760 mm; the diameter of the internal components of the transparent sphere is 1.0-6.0mm, and the internal components of the sphere are randomly and alternately distributed in the micro-reactor channel; the transparent spherical inner member is quartz beads or glass beads, preferably quartz beads.
7. The coupled photocatalytic controllable according to claim 1
The cationic polymerization method is characterized in that in the step (3), the microchannel reaction device further comprises a first feeding pump, a second feeding pump, a micro mixer and a receiver, wherein the first feeding pump and the second feeding pump are arranged in parallel and are simultaneously connected to the micro mixer, the microreactor and the receiver are sequentially arranged in series, the light source is arranged outside the microreactor pipeline, and the first feeding pump, the second feeding pump and the micro mixer are all subjected to shading treatment.
8. The coupled photocatalytic controllable cationic polymerization method according to claim 1, wherein in the step (4), the quenching agent is triethylamine, and the amount of the quenching agent is 1-5 times of the molar amount of the photocatalyst in the collected reaction solution; the organic solvent is selected from one or two of methanol or n-hexane, and the amount of the organic solvent is 20-100 times of the volume of the collected reaction liquid.
9. The method for coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in the step (4), the separation and purification method is: placing in a refrigerator at-20 deg.C for 15-25min, centrifuging, filtering for several times, air drying the obtained precipitate, and vacuum drying.
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