CN114539453B - Method for coupling photocatalytic controllable cationic polymerization - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 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 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000010791 quenching Methods 0.000 claims abstract description 13
- 230000000171 quenching effect Effects 0.000 claims abstract description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000010453 quartz Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 25
- 239000011324 bead Substances 0.000 claims description 19
- -1 2,4, 6-tri (p-tolyl) tetrafluoro pyridinium borate Chemical group 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
- 238000001914 filtration Methods 0.000 claims description 17
- 230000014759 maintenance of location Effects 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 16
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 26
- 238000002347 injection Methods 0.000 description 23
- 239000007924 injection Substances 0.000 description 23
- 238000009826 distribution Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 238000001542 size-exclusion chromatography Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000010183 spectrum analysis Methods 0.000 description 15
- 230000001105 regulatory effect Effects 0.000 description 14
- 238000001035 drying Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003756 stirring Methods 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
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011043 treated quartz Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 standby; (2) Dissolving alcohol and a photocatalyst in an organic solvent under the anhydrous inert gas atmosphere to obtain a mixed system for standby; (3) In a micro-channel reaction device, pumping the two mixed systems prepared in the steps (1) and (2) into a micro-reactor provided with a light source and a transparent sphere internal component at the same time, reacting under the illumination condition, and collecting a reaction liquid; (4) And (3) 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 the micro-reactor system containing the internal components to combine the photocatalytic cationic polymerization, greatly improves the mixing efficiency, shortens the reaction time, realizes the continuous production, and has the advantages of green, safety, high efficiency, quick 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 method for coupling photocatalytic controllable cationic polymerization.
Background
Microreactors have a larger specific surface area than conventional batch reactors, with advantages in organic chemistry and polymer synthesis, their large surface to volume ratio and continuous flow characteristics allowing improved momentum/mass/heat transfer and high level control of the reaction process. The use of continuous flow techniques under different polymerization mechanisms has been demonstrated to accelerate the polymerization rate, achieve narrower dispersity and higher chemoselectivity.
However, the conventional microreactor is characterized in that fluid passes through a tube with a reynolds number smaller than 2000 due to a laminar flow effect, and the result of the laminar flow is parabolic velocity distribution, and the reaction solution undergoes different retention times due to friction between an interface of a mobile phase and a fixed tube, so that the reaction solution has a certain side effect on polymer synthesis.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a method for coupling photocatalytic controllable cationic polymerization, which is used for strengthening the mass and heat transfer process of the prior micro-reaction technology so as to improve the controllability of the reaction.
The technical scheme is as follows: in order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method of coupling photocatalytic controlled cationic polymerization comprising the steps of:
(1) Vinyl monomer is dissolved in organic solvent under the condition of anhydrous inert gas atmosphere to obtain a mixed system for standby;
(2) Dissolving alcohol and a photocatalyst in an organic solvent under the anhydrous inert gas atmosphere to obtain a mixed system for standby;
(3) In a micro-channel reaction device, pumping the two mixed systems prepared in the steps (1) and (2) into a micro-reactor provided with a light source and a transparent sphere internal component at the same time, reacting under the illumination condition, and collecting a reaction liquid;
(4) And (3) 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, tertiary butanol and trifluoroethanol; the photocatalyst is 2,4, 6-tri (p-tolyl) tetrafluoro pyridinium borate; 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 amount of alcohol is 3.3-26% of the amount of vinyl monomer in mole percent; 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 reaction pipeline of the micro-reactor is made of high-permeability PFA material or quartz tube, the inner diameter of the pipeline is 1-10 mm, and the length of the pipeline is 90-760 mm; the diameter of the transparent sphere inner member is 1.0-6.0mm, and the sphere inner members are randomly and alternately distributed in the micro-reactor pipeline; the transparent sphere inner member is quartz bead or glass bead, preferably quartz bead.
Preferably, in step (3), the microchannel reactor further comprises a first feed pump, a second feed pump, a micromixer and a receiver, the first feed pump and the second feed pump are arranged in parallel and are simultaneously connected to the micromixer, the microreactor and the receiver are sequentially arranged in series, the light source is arranged outside a microreactor pipeline, and the first feed pump, the second feed pump and the micromixer are all subjected to shading treatment.
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 and n-hexane, and the dosage 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 the following steps: placing in a refrigerator at-20deg.C for 15-25min, centrifuging, filtering, circulating for several times, air drying the obtained precipitate, and vacuum drying
The invention can improve the fluid state in the micro-reaction pipeline, reduce the Poisson's fluid effect, form disturbance effect, enhance the mixing and mass and heat transfer efficiency of the micro-reactor, and promote the polymerization rate, so 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, for example, the size reaches the centimeter level, the flux of a micro-reaction system is increased, and the method has important significance for industrialization of continuous flow technology.
According to the invention, a micro-flow field technology is combined with a photocatalysis controllable cationic polymerization system, a micro-reaction unit is constructed aiming at a specific photocatalyst and a corresponding monomer, and the improvement of the polymerization reaction rate and the optimization of the molecular weight distribution index are realized; the inner member is used to make the fluid in the pipeline form disturbance, so that the mass transfer and heat transfer efficiency of the micro-flow field technology is enhanced, the accurate space-time positioning of the cationic monomer is carried out, the structure of the homopolymer is accurately constructed, and finally the homopolymer with controllable structure and chain length is obtained. The method provides a new technical reference for continuous-flow controllable cationic polymerization and also provides a good reference for light-mediated polymerization in a microreactor.
The beneficial effects are that: compared with the traditional kettle type reactor and the traditional microreactor, the invention breaks through plug flow by utilizing the novel method of coupling controllable cationic polymerization of the microreactor with the inner member, strengthens excellent mixing and mass and heat transfer efficiency and reaction process of the microreactor, improves polymerization reaction rate, shortens reaction time, obtains a polymer with narrower molecular weight distribution index, can better control reaction conditions, and is expected to be applied to industrial production.
Drawings
FIG. 1 is a schematic diagram of a microchannel module reactor and internals microreaction piping, comprising: sample introduction devices 1, 2, a micromixer 3, an illumination device 4 and a product collector 5.
FIG. 2 is a GPC chart of the resulting polymer being the polyoxymethylene styrene (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 the PMP of example 1 1 H NMR chart.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail 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.
GPC column detection using a Wyatt size exclusion chromatography system formulated with an SSI 1500 pump, a Wyatt Optilabrex detector, waters Styragel HR;
analysis conditions: the mobile phase is tetrahydrofuran, the flow rate is 0.7mL/min, the column temperature is 35 ℃, and the sample injection volume is 0.4mL.
Sample measurement: 4mg of pure sample is taken in a centrifuge tube, 1mL of tetrahydrofuran solution is added for dilution, and 4mL of solution is taken for measurement after filtration by using a disposable filter head (containing a 0.33um organic filter membrane).
In the following examples of the invention, the conversion C represents the molar ratio of the reacted monomers to the total amount of the initial monomers and can be obtained by the following calculation method:
C＝(n a /n 0 )*100％
wherein C represents the conversion of the monomerRate, n a Represents the molar quantity of the monomer, n 0 Indicating the total molar amount of the initial monomers.
The adopted micro-channel reaction device comprises a first feed pump (material sample injection device 1), a second feed pump (material sample injection device 1), a micro-mixer 3, a micro-reactor and a receiver (product collector 5), wherein the first feed pump and the second feed pump are arranged in parallel and are simultaneously connected to the micro-mixer 3, the micro-reactor and the receiver are sequentially connected in series, the illumination device 4 is arranged outside a micro-reactor pipeline, and the first feed pump, the second feed pump and the micro-mixer 3 are all subjected to shading treatment. The quartz bead sphere inner members are randomly and alternately distributed in the micro-reactor pipeline.
Example 1
4-methoxystyrene (2.02 g,15 mmol), methylene chloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%), methylene chloride (12.6 mL) were added to two reaction bottles after anhydrous anaerobic treatment respectively, shaking and mixing were then transferred to the first material sample injection device 1 and the second material sample injection device 2, the flow rates of 1 and 2 were regulated to 0.3mL/min, the selected pipe was a quartz tube with an inner diameter of 2mm, the selected added internal member was quartz beads with a diameter of 1mm, the retention volume was 4mL, the reaction temperature of the reactor was 25 ℃, the light source was turned on to start the reaction, the light wavelength was 450nm, 2mL was collected after 7min of reaction was stabilized, 0.2mL of triethylamine and 80mL of methanol were sequentially added, and the mixture was placed in a refrigerator with a temperature of-20 ℃ for 20min, the mixture was subjected to centrifugal filtration and circulated 3 times, the obtained white precipitate was dried in a vacuum oven and placed in a drying oven for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has the number average molecular weight of 5100g/mol, the molecular weight distribution index of 1.10 and the conversion rate of 99 percent.
Example 2
4-methoxystyrene (4.04 g,30 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, shaking and mixing are carried out, the mixture is transferred into a first material sample injection device 1 and a second material sample injection device 2, the flow rates of 1 and 2 are regulated and controlled to be 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 3mm, the selected added internal components are quartz beads with the diameter of 1mm, the retention volume is 6mL, the reaction temperature of the reactor is 25 ℃, a light source is started to react, the light wavelength is 450nm, 2mL is collected after the reaction is stable for 10min, 0.2mL of a quenching agent, 0.2mL of triethylamine and 80mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is circulated for 3 times, the obtained white precipitate is dried in a vacuum box for 48h after the air drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 12100g/mol, a molecular weight distribution index of 1.24 and a conversion rate of 97%.
Example 3
4-methoxystyrene (10.1 g,75 mmol), methylene chloride (25.2 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%), methylene chloride (25.2 mL) were added to two reaction bottles after anhydrous anaerobic treatment respectively, shaking and mixing were then transferred to the first material sample injection device 1 and the second material sample injection device 2, the flow rates of 1 and 2 were regulated to 0.3mL/min, the selected pipe was a quartz tube with an inner diameter of 8mm, the selected added internal member was quartz beads with a diameter of 1mm, the retention volume was 9mL, the reaction temperature of the reactor was 25 ℃, the light source was turned on to start the reaction, the light wavelength was 450nm, 2mL was collected after 15min of reaction was stabilized, 0.2mL of triethylamine and 80mL of methanol were sequentially added, and the mixture was placed in a refrigerator with a temperature of-20 ℃ for 20min, the mixture was subjected to centrifugal filtration and circulated 3 times, the obtained white precipitate was dried in a vacuum oven and placed in a drying oven for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 25400g/mol, a molecular weight distribution index of 1.26 and a conversion rate of 97%.
Example 4
4-methoxystyrene (20.2 g,150 mmol), methylene chloride (25.2 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%), methylene chloride (25.2 mL) were added to two reaction bottles after anhydrous anaerobic treatment respectively, shaking and mixing were then transferred to the first material sample injection device 1 and the second material sample injection device 2, the flow rates of 1 and 2 were regulated to 0.3mL/min, the selected pipe was a quartz tube with an inner diameter of 10mm, the selected added internal member was quartz beads with a diameter of 1mm, the retention volume was 15mL, the reaction temperature of the reactor was 25 ℃, the light source was turned on to start the reaction, the light wavelength was 450nm, 2mL was collected after the reaction was stabilized for 25min, 0.2mL of triethylamine and 80mL of methanol were sequentially added, and placed in a refrigerator with a temperature of-20 ℃ for 20min, the centrifugal filtration was circulated 3 times, and the obtained white precipitate was placed in a vacuum drying box for 48h after the air drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 52400g/mol, a molecular weight distribution index of 1.29 and a conversion rate of 96%.
Example 5
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, shaking and mixing are carried out, the flow rates of 1 and 2 are regulated to be 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 2mm, the selected added internal components are quartz beads with the diameter of 1.5mm, the retention volume is 4mL, the reaction temperature of the reactor is 25 ℃, a light source is turned on for reaction, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.2mL of a quencher, 80mL of triethylamine and 20 mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is circulated for 3 times, the obtained white precipitate is dried in a vacuum drying box after being placed into a vacuum drying box for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 4900g/mol, a molecular weight distribution index of 1.15 and a conversion rate of 94%.
Example 6
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, shaking and mixing are carried out, the flow rates of 1 and 2 are regulated to be 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 3mm, the retention volume is 6mL, the selected added internal components are quartz beads with the diameter of 1mm, the reaction temperature of the reactor is 25 ℃, the light source is started to react, the light wavelength is 450nm, 2mL is collected after the reaction is stable, 0.2mL of a quenching agent and 80mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is circulated for 3 times, and the obtained white precipitate is placed into a vacuum drying box for 48h after the air drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 4900g/mol, a molecular weight distribution index of 1.18 and a conversion rate of 92%.
Example 7
4-methoxystyrene (2.02 g,15 mmol), methylene chloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%), methylene chloride (12.6 mL) were added to two reaction bottles after anhydrous anaerobic treatment respectively, shaking and mixing were then transferred to the first material sample injection device 1 and the second material sample injection device 2, the flow rates of 1 and 2 were regulated to 0.3mL/min, the selected pipe was a quartz tube with an inner diameter of 3mm, the selected added internal member was quartz beads with a diameter of 2mm, the retention volume was 4mL, the reaction temperature of the reactor was 25 ℃, the light source was turned on to start the reaction, the light wavelength was 450nm, 2mL was collected after 7min of reaction was stabilized, 0.2mL of triethylamine and 80mL of methanol were sequentially added, and the mixture was placed in a refrigerator with a temperature of-20 ℃ for 20min, the mixture was subjected to centrifugal filtration and circulated 3 times, the obtained white precipitate was dried in a vacuum oven for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 5300g/mol, a molecular weight distribution index of 1.20 and a conversion rate of 90%.
Example 8
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, shaking and mixing are carried out, the flow rates of 1 and 2 are regulated to be 0.4mL/min, a selected pipeline is a quartz tube, the inner diameter is 2mm, the selected added internal components are treated quartz beads with the diameter of 1mm, the retention volume is 6mL, the reaction temperature of the reactor is 25 ℃, a light source is started to react, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.2mL of a quenching agent, 80mL of methanol and 80mL of the quenching agent are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is circulated for 3 times, the obtained white precipitate is dried in a vacuum drying box and placed into a vacuum drying box for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 5200g/mol, a molecular weight distribution index of 1.06 and a conversion rate of 100%.
Example 9
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (16 mg,0.5mmol,3.3 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, the flow rates of 1 and 2 are regulated to 0.3mL/min, the selected pipeline is a quartz tube, the inner diameter is 2mm, the selected added internal components are quartz beads with the diameter of 1mm, the retention volume is 4mL, the reaction temperature of the reactor is 25 ℃, the light source is started to react, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.2mL of a quenching agent, 80mL of methanol and the quenching agent are sequentially added, the mixture is placed into a refrigerator with the temperature of-20 ℃ for 20min, centrifugal filtration is circulated for 3 times, the obtained white precipitate is dried in a vacuum drying box for 48h after shaking and mixing. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 4700g/mol, a molecular weight distribution index of 1.26 and a conversion rate of 86%.
Example 10
4-methoxystyrene (2.02 g,15 mmol), methylene chloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), ethanol (46 mg,1mmol,6.5 mol%) and methylene chloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, the mixture is transferred into a first material sample injection device 1 and a second material sample injection device 2 after shaking and mixing, the flow rates of 1 and 2 are regulated to 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 2mm, the selected added internal components are quartz beads with the diameter of 1mm, the retention volume is 4mL, the reaction temperature of the reactor is 25 ℃, a light source is started to react, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.2mL of a quenching agent, 80mL of triethylamine and 80mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is circulated for 3 times, the obtained white precipitate is dried in a vacuum box for 48h after drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 5900g/mol, a molecular weight distribution index of 1.29 and a conversion rate of 88%.
Example 11
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), isopropanol (60 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, the stirring and mixing are carried out, the mixture is transferred into a first material sample injection device 1 and a second material sample injection device 2, the flow rates of 1 and 2 are regulated and controlled to be 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 2mm, the selected added internal components are quartz beads with the diameter of 1mm, the retention volume is 4mL, the reaction temperature of the reactor is 25 ℃, a light source is started to react, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.2mL of a quencher, 0.2mL of triethylamine and 80mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is circulated for 3 times, the obtained white precipitate is placed into a vacuum precipitation box for drying for 48h after the air drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 6900g/mol, a molecular weight distribution index of 1.33 and a conversion rate of 97%.
Example 12
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), tert-butyl alcohol (74 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, the stirring and mixing are carried out, the mixture is transferred into a first material sample injection device 1 and a second material sample injection device 2, the flow rates of 1 and 2 are regulated and controlled to be 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 2mm, the selected added internal components are quartz beads with the diameter of 1mm, the retention volume is 4mL, the reaction temperature of the reactor is 25 ℃, the light source is started to react, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.2mL of a quencher, 0.2mL of triethylamine and 80mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration is carried out for 3 times, the obtained white precipitate is placed into a vacuum precipitation box for drying for 48h after the air drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has the number average molecular weight of 5100g/mol, the molecular weight distribution index of 1.32 and the conversion rate of 97 percent.
Example 13
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (16.7 mg,0.19mmol,1.25 mol%), methanol (32 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, shaking and mixing uniformly, then the mixture is transferred into a first material sample injection device 1 and a second material sample injection device 2, the flow rates of 1 and 2 are regulated and controlled to be 0.3mL/min, a selected pipeline is a quartz tube, the inner diameter is 2mm, half of the selected added internal components are quartz beads with the diameter of 1mm, the retention volume is 4mL, the reaction temperature of the reactor is 25 ℃, a light source is started to react, the light wavelength is 450nm, 2mL is collected after 7min of reaction is stable, 0.1mL of a quencher and 80mL of methanol are sequentially added, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for 20min, centrifugal filtration and circulated for 3 times, the obtained white precipitate is placed into a vacuum precipitation box for drying for 48h after the air drying. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 4100g/mol, a molecular weight distribution index of 1.18 and a conversion rate of 72%.
Comparative example 1
To the two reaction flasks after the anhydrous anaerobic treatment were added 4-methoxystyrene (2.02 g,15 mmol), methylene chloride (25.2 mL), pyridinium 2,4, 6-tris (p-tolyl) tetrafluoroborate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%) in this order, and the mixture was stirred and mixed. The reaction temperature is 25 ℃, a light source is started to react, the illumination wavelength is 450nm, 2mL of reaction liquid is collected after the reaction is stabilized for 20min, 0.2mL of quencher triethylamine and 80mL of methanol are sequentially added, the mixture is placed in a refrigerator at the temperature of minus 20 ℃ for 20min, centrifugal filtration is performed for 3 times, and the obtained white precipitate is dried in air and then placed in a vacuum drying oven for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has the number average molecular weight of 6100g/mol, the molecular weight distribution index of 1.36 and the conversion rate of 96%.
Comparative example 2
4-methoxystyrene (2.02 g,15 mmol), methylene dichloride (12.6 mL) and 2,4, 6-tris (p-tolyl) tetrafluoropyridinium borate (33.4 mg,0.38mmol,2.5 mol%), methanol (32 mg,1mmol,6.5 mol%) and methylene dichloride (12.6 mL) are respectively added into two reaction bottles subjected to anhydrous anaerobic treatment, the mixture is stirred and mixed uniformly, the mixture is transferred into a first material sample injection device 1 and a second material sample injection device 2, the flow rates of 1 and 2 are regulated to be 0.3mL/min, the selected pipeline is a quartz tube (no inner member), the inner diameter is 1mm, the retention volume is 6mL, the reaction temperature of the reactor is 25 ℃, the light source is started to react, the light wavelength is 450nm, 2mL is collected after the reaction is stabilized for 10min, 0.2mL of a quenching agent and 80mL of methanol are added, the mixture is placed into a refrigerator at-20 ℃ for 20min, the mixture is centrifugally filtered and circulated for 3 times, and the obtained white precipitate is dried in air in a vacuum drying box for 48h. The PMP polymer product obtained by size exclusion chromatography and nuclear magnetic hydrogen spectrum analysis has a number average molecular weight of 5700g/mol, a molecular weight distribution index of 1.22 and a conversion rate of 94%.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. A method of coupling photocatalytic controlled cationic polymerization comprising the steps of:
(1) Vinyl monomer is dissolved in organic solvent under the condition of anhydrous inert gas atmosphere to obtain a mixed system for standby;
(2) Dissolving alcohol and a photocatalyst in an organic solvent under the anhydrous inert gas atmosphere to obtain a mixed system for standby;
(3) In a micro-channel reaction device, pumping the two mixed systems prepared in the steps (1) and (2) into a micro-reactor provided with a light source and a transparent sphere internal component at the same time, reacting under the illumination condition, and collecting a reaction liquid; the inner diameter of the pipeline is 1-10 mm, and the length of the pipeline is 90-760 mm; the diameter of the transparent sphere inner member is 1.0-6.0mm; the components in the spheres are randomly and alternately distributed in the micro-reactor pipeline;
(4) And (3) 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 of coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in step (1), the vinyl-based monomer is 4-methoxystyrene; the organic solvent is one or more of dichloromethane and dichloroethane.
3. The method of coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in step (2), the alcohol is one or more of methanol, ethanol, isopropanol, t-butanol, trifluoroethanol; the photocatalyst is 2,4, 6-tri (p-tolyl) tetrafluoro pyridinium borate; the organic solvent is one or more of dichloromethane and dichloroethane.
4. The method of coupled photocatalytic controlled cationic polymerization according to claim 1, characterized in that in step (3), the molar ratio of vinyl monomer to alcohol is 10-400:1; in the mixed system obtained in the step (1), the concentration of the vinyl monomer is 0.3-3 mol/L.
5. The method of coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in step (3), the reaction flow rate of the reaction is 0.1 to 0.8mL/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 method for coupling photocatalytic controllable cationic polymerization according to claim 1, wherein in the step (3), the material of the reaction tube of the microreactor is high-permeability PFA material or quartz tube; the transparent sphere inner member is quartz beads or glass beads.
7. The method of coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in the step (3), the microchannel reaction apparatus further comprises a first feed pump, a second feed pump, a micromixer and a receiver, the first feed pump and the second feed pump are arranged in parallel and simultaneously connected to the micromixer, the microreactor and the receiver are arranged in series in order, the light source is arranged outside a pipe of the microreactor, and the first feed pump, the second feed pump and the micromixer are all subjected to light shielding treatment.
8. The method for coupling photocatalytic controlled cationic polymerization according to claim 1, characterized in that in step (4), the quencher is triethylamine, and the amount of the quencher is 1 to 5 times the molar amount of the photocatalyst in the collected reaction solution; the organic solvent is selected from one or two of methanol and n-hexane, and the dosage of the organic solvent is 20-100 times of the volume of the collected reaction liquid.
9. The method of coupled photocatalytic controlled cationic polymerization according to claim 1, wherein in step (4), the separation and purification method is as follows: placing in a refrigerator at-20deg.C for 15-25min, centrifuging, filtering, circulating for several times, air drying the obtained precipitate, and vacuum drying.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201046394Y (en) * | 2007-05-21 | 2008-04-16 | 中国科学院过程工程研究所 | A novel disturbed flow type complex component for circulating fluidized bed effector |
| JP2009067999A (en) * | 2007-08-21 | 2009-04-02 | Kyoto Univ | METHOD FOR PRODUCING POLYMER HAVING Mw/Mn OF 1.25 OR LOWER |
| JP2014087752A (en) * | 2012-10-30 | 2014-05-15 | Toray Eng Co Ltd | Microreactor system, method of producing compound using the same, and method of producing alkenyl phosphorus compound |
| CN105617957A (en) * | 2014-10-27 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method for strengthening mixing and reaction of fluids in micro-reactor |
| CN111777540A (en) * | 2020-07-23 | 2020-10-16 | 南京工业大学 | Method for synthesizing pyrrolidone compound by continuous light-induced catalysis |
| CN112058192A (en) * | 2020-09-04 | 2020-12-11 | 湖南大学 | Continuous flow micro-reactor, manufacturing method and application |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201046394Y (en) * | 2007-05-21 | 2008-04-16 | 中国科学院过程工程研究所 | A novel disturbed flow type complex component for circulating fluidized bed effector |
| JP2009067999A (en) * | 2007-08-21 | 2009-04-02 | Kyoto Univ | METHOD FOR PRODUCING POLYMER HAVING Mw/Mn OF 1.25 OR LOWER |
| JP2014087752A (en) * | 2012-10-30 | 2014-05-15 | Toray Eng Co Ltd | Microreactor system, method of producing compound using the same, and method of producing alkenyl phosphorus compound |
| CN105617957A (en) * | 2014-10-27 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method for strengthening mixing and reaction of fluids in micro-reactor |
| CN111777540A (en) * | 2020-07-23 | 2020-10-16 | 南京工业大学 | Method for synthesizing pyrrolidone compound by continuous light-induced catalysis |
| CN112058192A (en) * | 2020-09-04 | 2020-12-11 | 湖南大学 | Continuous flow micro-reactor, manufacturing method and application |
Non-Patent Citations (1)
| Title |
|---|
| Visible light photoinitiated metal-free living cationic polymerization of 4-methoxystyrene;Andrew J. Perkowski;《Journal of the American Chemical Society》;7580-7583 * |
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