CN109942733A - A kind of method that continuous flow moves synthetic polymer - Google Patents
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Abstract
The invention belongs to polymer synthesis techniques field, the method for the dynamic synthetic polymer of specially a kind of continuous flow.The present invention uses the continuous flowing polymerization of heating or illumination, using (methyl) acrylate, (methyl) fluoroalkyl acrylate, acrylamide and its derivative, Styrene and its derivatives as polymerized monomer, using sulfocarbonate, alkyl halide, perfluoroalkyl iodides as initiator, using heat or launch wavelength be 390 ~ 700 nm visible light as implementation means, reactant is heated or irradiated in organic solvent, obtains homopolymer or copolymer.Polymerization result shows that the flowing polymerization has good controllability to polymer number-average molecular weight, molecular weight distribution, chain end activity.The method of the present invention has many advantages, such as that easy to operate, suitable monomers range is wide, polymerization rate is fast and is easily achieved different scales synthesis.
Description
Technical field
The invention belongs to polymer synthesis techniques fields, and in particular to a kind of method that continuous flow moves synthetic polymer.
Background technique
Controlled Living Radical Polymerization combines the advantages of both conventional free radical polymerization and active anionic polymerization, can
The polymer that adjustable molecular weight, narrow molecular weight distribution are prepared under comparatively gentle reaction condition, in past 30 years rapidly
Develop into synthesis have precision architecture polymer reliable method [Chem. Rev., 2016, 116, 835; Chem. Rev., 2009, 109, 4963; Prog. Polym. Sci.2007, 32, 93.].Controlled Living Radical Polymerization can
The various polymer containing functional group are synthesized, product has the characteristics that controllable molecular weight, narrow molecular weight distribution, chain structure are accurate
[Macromolecules, 2012, 45, 4015; Chem. Rev., 2001, 101, 2921; Science, 2011,
333, 1104; Chem. Rev., 2009, 109, 5437; Chem. Rev., 2009, 109, 5402.].Based on upper
Reason is stated, using the method for Controlled Living Radical Polymerization, scientists can obtain having various chemical structures, physical property
Advanced polymer material, in various fields such as nanotechnology, biomedicine, the energy and national defence by more and more researchers'
Concern [J. Am. Chem. Soc., 2014, 136, 6513]。
Implement Controlled Living Radical Polymerization mainly have two kinds of means of light and heat [J. Am. Chem. Soc. 2011,
133, 9278; Nat. Chem.2009, 1, 133.].However, two kinds of means are in the extensive accurate complicated polymerization of synthesis
All there is certain limitation during object.For example, the continuous amplification with reaction vessel scale from laboratory to industry, passes
The external conditions such as matter, heat transfer gradually change, and the same polymer of synthesis can not be achieved the purpose that by simple replication reaction condition,
To influence properties of product and use.Therefore, there is an urgent need to develop one kind can control well polymeric articles quality and
Facilitate and realizes different scales synthetic method.
In recent years, continuous flow process receives the extensive concern of academia and industry, which is easy to since it has
Amplification, excellent mass-and heat-transfer ability, automated manufacturing easy to accomplish and production process the advantages that the safety is improved and be considered
Be produce small molecule and polymer practical and robust way [Chem. Soc. Rev., 2013, 42, 8849].By
High surface area/volume ratio in microchannel in continuous flow reactor, flow technique can be such that reaction solution obtains more uniformly
Heated/irradiation [Chem. Rec., 2014, 14, 410; Chem. Eur. J., 2014, 20, 10562.].Connect at present
Afterflow process is successfully used for small-molecule drug and the pharmaceutical intermediate synthesis (patent No.: CN 103275112A; CN
103755777; Angew. Chem, 2015,127,265).For example, Seeberger realizes anti-malaria medicaments qinghaosu
Flowing chemical synthesis (patent No.: CN 103764660B).For continuous flow method in Polymer Synthesizing application also in
Starting stage.In spite of patent report continuous flow emulsion polymerizing preparation aniline (patent publication No.: EP 3156122A1, US
9751983B2) and cross-linked polymer nano particle (patent publication No.: US 2005/0080209A1) is produced, but for being connected
Afterflow polymerization reaction is also rarely reported.
Based on the above reasons, the present invention provides a kind of versatile poly- (methyl) acrylic ester monomers, poly- of preparing
Controllable free-radical under the flox conditions of polymer such as (methyl) fluoroalkyl base ester, polyacrylamide and polystyrene type
Polymerization produces polymer for different scales and provides a kind of simple and easy method.
Summary of the invention
The object of the present invention is to provide a kind of method that continuous flow moves synthetic polymer, this method has easy to operate, suitable
With monomer range is wide, polymerization rate is fast and is easy to the advantages that different scales produce.
The method that continuous flow provided by the invention moves synthetic polymer, it is poly- using traditional heating or photocontrol living radical
It closes, monomer used is (methyl) acrylate, (methyl) fluoroalkyl acrylate, acrylamide and its derivative, styrene
And its one of derivative etc., initiator are one of alkyl halide, sulfocarbonate or perfluoroalkyl iodides, light-operated free radical
Used photocatalysis agent is small organic molecule photochemical catalyst in polymerization, the light conditions for being 390 ~ 700 nm in heating or launch wavelength
Under, the reactant in flow duct is heated or irradiated, the homopolymer or block copolymer of molecular weight needed for preparing.Synthesis
Equipment therefor includes modular pump, transparent pipeline, heating or illumination apparatus and collection of products device；Specific step is as follows:
(1) reaction solution is prepared, is under stiring uniformly mixed each component, and removes the oxygen in reaction system.The reaction is molten
Liquid is divided into following three kinds of situations:Reaction solution A contains monomer, initiator, additive, solvent；Reaction solution B, contains
Monomer, initiator, catalyst, solvent；Reaction solution C, containing for monomer, initiator, photochemical catalyst, solvent；By mole
Than meter, monomer: initiator=1000: (1 ~ 100), the wherein light in the catalyst in reaction solution B and reaction solution C
Catalyst is 0.005 ~ 5 mol% of monomer；
(2) reaction mixture is transferred in modular pump, certain flow velocity (5 ~ 500 μ L/min) is set, reaction mixture is allowed to exist
The pipe reaction container that certain length (1.5 ~ 20 m) is flowed through under heating condition or under the illumination condition of different wave length, is being received
Corresponding reaction solution is obtained in acquisition means；Wherein, reaction solution A and reaction solution B is suitable for heating reaction, reaction solution C
Suitable for illumination reaction；
(3) by reaction solution purifying, processing, poly- (methyl) acrylate, poly- (methyl) fluoroalkyl acrylate, poly- third are obtained
Acrylamide and its derivative and one of polystyrene and its derivative.
In the present invention, additive is using azo as the compound of skeleton in the reaction solution A；In the reaction solution B
Catalyst is the complex that copper or iron and nitrogen ligand are formed；In the reaction solution C photochemical catalyst be porphyrin, dihydrophenazine,
One or more of phenoxazine, organic micromolecule compound that phenthazine is skeleton.
In the present invention, the reaction dissolvent is dimethyl sulfoxide,N, NDimethylformamide,N, NDimethylacetamide
Amine,NOne of methyl pyrrolidone, acetonitrile are a variety of.
In the present invention, the initiator is one of alkyl halide, sulfocarbonate or perfluoroalkyl iodides, initiator knot
Shown in structure such as following formula (1), (2) or (3):
Wherein, in formula (1), R1For carbon atom number be 1 ~ 12 aliphatic group, aromatic group, the alkane that carbon atom number is 1 ~ 12
The dialkyl amido that the alkoxy, aryloxy group, carbon atom number that base sulfydryl, aryl thiol, carbon atom number are 1 ~ 12 are 1 ~ 12；R2For
Hydrogen atom, the alkyl that carbon atom number is 1 ~ 12；R3For carbon atom number be 1 ~ 12 alkyl, aryl；R4It is 1 ~ 12 for carbon atom number
Alkoxy carbonyl, the fluoroalkoxycarbonylgroups that carbon atom number is 1 ~ 12, aryloxycarbonyl, itrile group, the alkane that carbon atom number is 1 ~ 12
Base amino carbonyl；X is bromine or iodine；In formula (2), n is the integer between 0 ~ 12；In formula (3), R5For hydrogen, alkyl or aryl, R6For
Hydrogen, alkyl or aryl, R7For hydrogen, alkyl or aryl, X is Cl or Br atom.
In the present invention, it is (methyl) acrylate, (methyl) fluoroalkyl acrylate, acryloyl that the monomer, which is selected from,
The types such as amine and its derivative, Styrene and its derivatives, shown in monomer structure such as following formula (4) ~ (6):
Wherein: in formula (4), R1For hydrogen atom or methyl, R2The aliphatic alkyl or hydroxy alkyl, virtue for being 1 ~ 18 for carbon atom number
Fragrant race's group；In formula (5), R3For hydrogen atom or methyl, R4For carbon atom number be 1 ~ 18 perfluoroalkyl or containing a small number of hydrogen atoms
Containing fluoroalkyl, n is 1 ~ 3 direct integer；In formula (6), R5The aliphatic alkyl for being 1 ~ 3 for hydrogen atom or carbon atom number, R6For hydrogen
The aliphatic alkyl that atom or carbon atom number are 1 ~ 3.
Flowing polymerization according to the present invention includes heating and two kinds of illumination, heats the temperature range of reaction in room temperature
~ 120 DEG C, the light source that illumination reaction is 390 ~ 700 nm using launch wavelength, reaction mixture residence time in flow channel
And polymerization reaction time is 0.5 ~ 10 hour.
The method that the continuous flow involved in the present invention arrived moves synthetic polymer can also lead in addition to that can prepare homopolymer
It crosses following operation preparation block copolymer: after first segment monomer polymerization, not allowing it to enter collection device, but enter the
Two sections of flowing reactive pipelines terminate place's connection hybrid juction in first segment pipeline, access second modular pump, be pumped into second segment list
Continue to react in pipe reaction container after body, can be obtained block copolymerization in second segment pipe reaction container exit
Object.
The present invention has the following advantages that and characteristic:
Successfully continuous current method is applied in Controlled Living Radical Polymerization reaction, it is living using traditional heating or photocontrol
The polymerization of free love base, this method is easy to operate, suitable monomers range is wide, polymerization rate is fast and is easy to different scales production etc.
Advantage.
Detailed description of the invention
Fig. 1 is that continuously flowing prepares homopolymer and copolymer schematic device for illumination.
Fig. 2 is hexafluorobutyl acrylate monomer1H NMR,19F NMR spectra.
Fig. 3 is (A) the GPC figure and (B) of embodiment 41H NMR spectra.
Fig. 4 is (A) the GPC figure and (B) of embodiment 91H NMR、19F H NMR spectroscopy.
Specific embodiment
The present invention is described in detail below with reference to part specific embodiment, these embodiments are merely to illustrate the present invention,
Rather than limit the scope of the invention, the preparation method in embodiment is only preferred embodiment, but the invention is not limited to excellent
Select preparation method.For the same reaction, reaction condition parameter can not changed by adjusting acquisition time or parallel reaction device
In the case where realize different scales polymer synthesis.
First part: continuous flow dynamic circuit connector is at homopolymer
Embodiment 1: using reaction solution A, heats continuous flowing preparationN, NDimethylacrylamide homopolymer
It pressesN, NDimethylacrylamide: 2-(((hexyl is thio) thio carbonic acyl radical) thio) -2 Methylpropionic acid: azo
Bis-isobutyronitrile=10000: 100: 1 molar ratio is by 20 mmol of above-mentioned raw materials, 0.2 mmol, 2 × 10-3Mmol points
It is not added in the bottle equipped with magneton, 5 mL DMF is added, reaction mixture are removed into oxygen after stirring and dissolving is uniform, then
It is transferred to modular pump, internal diameter is passed through under the conditions of at 65 DEG C by reactant solution as 2.4 millimeters, length with the flow velocity of 500 μ L/min
20 meters of reaction microchannel, exit obtain solution after reaction, pass through1It is 95% that H NMR, which measures monomer conversion, sample
Product are precipitated with ether, are dried under vacuum to constant weight, obtain faint yellow solid.The polymer molecular weight that GPC is measuredM n = 9.40 ×
103G/mol and molecular weight distributionM w/M n= 1.08.By this flow velocity, continuous 24 h of reaction solution that collects can be gatheredN, N- two
274 g of Methacrylamide, molecular weight distribution 1.08.Each reaction member occupied area is about 0.3 m2, it calculates accordingly,
10 m2Area in, in parallel can be no less than 30 modular pumps, can accurately synthesize within continuous work one month poly-N, NDimethyl
Acrylamide is no less than 245 kg.Expand the strategy of combined coefficient with reaction unit in parallel together by extending acquisition time in this way
Sample is suitable for the synthesis of this paper other polymers.
Embodiment 2: reaction solution B is used, continuous flowing is heated and prepares imperplex
By methyl methacrylate: alpha-brominated ethyl isobutyrate: cuprous bromide: bipyridyl=100: 1: 1: 2
Molar ratio 20 mmol of above-mentioned raw materials, 0.2 mmol, 0.2 mmol, 0.4 mmol are added separately to the bottle equipped with magneton
In, 10 mL DMSO are added, reaction mixture is removed into oxygen after stirring and dissolving is uniform, is subsequently transferred to modular pump, with 100 μ
The flow velocity of L/min is 2.4 millimeters long 4 meters of reaction microchannel, exit by internal diameter under the conditions of 100 DEG C by reactant solution
Solution after reaction is obtained, is passed through1It is 89% that H NMR, which measures monomer conversion, and sample methanol extraction is dried under vacuum to
Constant weight obtains white solid.The polymer molecular weight that GPC is measuredM n = 8.60 × 103G/mol and molecular weight distributionM w/M n
= 1.15。
Embodiment 3: reaction solution B is used, continuous flowing is heated and prepares styrene homopolymers
By styrene: 1- phenylethyl bromine: cuprous bromide: three (2- dimethylaminoethyl) amine=200: 2: 1:
20 mmol of above-mentioned raw materials, 0.2 mmol, 0.1 mmol, 0.1 mmol are added separately to the bottle equipped with magneton by 1 molar ratio
In, 10 mL NMP are added, reaction mixture is removed into oxygen after stirring and dissolving is uniform, is subsequently transferred to modular pump, with 50 μ L/
The flow velocity of min is 2.4 millimeters long 8 meters of reaction microchannel by internal diameter under the conditions of 120 DEG C by reactant solution, and exit obtains
To solution after reaction, pass through1It is 85% that H NMR, which measures monomer conversion, and sample methanol extraction is dried under vacuum to perseverance
Weight, obtains white solid.The polymer molecular weight that GPC is measuredM n = 8.70 × 103G/mol and molecular weight distributionM w/M n =
1.20。
Embodiment 4: reaction solution C is used, continuously flowing prepares hexafluorobutyl acrylate homopolymer for illumination
By hexafluorobutyl acrylate: 2-(((own sulfenyl) is thio) is thio) ethyl propionates: 3,7- bis- (4- butyl phenyls)-
Phenthazine=2000 10- phenyl -10H-: 20: 1 molar ratio by 5 mmol of above-mentioned raw materials, 0.05 mmol, 2.5 ×
10-3Mmol is added separately in the bottle equipped with magneton, and 5 mL DMSO are added, take off reaction mixture after stirring and dissolving is uniform
Except oxygen, it is subsequently transferred to modular pump, is led under the irradiation of 13 W white led lamps with the flow velocity of 50 μ L/min by reactant solution
Crossing internal diameter is 1.2 millimeters long 1.6 meters of reaction microchannel, and exit obtains solution after reaction, passes through1H NMR is measured
Monomer conversion is 86%, and the mixing liquid precipitate for the first alcohol and water that sample volume ratio is 1: 1 three times, is dried under vacuum to constant weight,
Obtain faint yellow solid.The polymer molecular weight that GPC is measuredM n = 9.60 × 103G/mol and molecular weight distributionM w/M n =
1.05。
Embodiment 5: reaction solution C is used, continuously flowing prepares methyl acrylate homopolymer for illumination
By methyl acrylate: 4- cyano -4-(((hexyl is thio) thio carbonic acyl radical) thio) ethyl valerate: tetraphenylporphyrin
Zinc=20000: 100: 1 molar ratio is by 20 mmol of above-mentioned raw materials, 0.1 mmol, 1 × 10-3Mmol is separately added into
Into the bottle equipped with magneton, 10 mL DMSO are added, reaction mixture is removed into oxygen after stirring and dissolving is uniform, then shifts
To modular pump, internal diameter is passed through under the irradiation of 13 W white led lamps by reactant solution as 1.2 millimeters with the flow velocity of 200 μ L/min
Long 8.2 meters of reaction microchannel, exit obtains solution after reaction, passes through1It is 90% that H NMR, which measures monomer conversion,
Sample three times, is dried under vacuum to constant weight with methanol extraction, obtains faint yellow solid.The polymer molecular weight that GPC is measuredM n =
1.60 × 104G/mol and molecular weight distributionM w/M n = 1.15。
Embodiment 6: using reaction solution C, and preparation is continuously flowed in illuminationN, NDimethylacrylamide homopolymer
It pressesN, NDimethylacrylamide: 2-(((hexyl is thio) thio carbonic acyl radical) thio) -2 Methylpropionic acid: three (2-
Phenylpyridine) close iridium=10000: 100: 1 molar ratio is by 20 mmol of above-mentioned raw materials, 0.2 mmol, 2 × 10-3
Mmol is added separately in the bottle equipped with magneton, and 10 mL DMF are added, reaction mixture is removed oxygen after stirring and dissolving is uniform
Gas is subsequently transferred to modular pump, with the flow velocity of 100 μ L/min by reactant solution under the irradiation of 13 W white led lamps by interior
Diameter is 1.2 millimeters long 4 meters of reaction microchannel, and exit obtains solution after reaction, passes through1H NMR measures monomer and turns
Rate is 92%, and sample ether precipitates three times, is dried under vacuum to constant weight, obtains faint yellow solid.The polymer that GPC is measured point
Son amountM n = 9.20 × 103G/mol and molecular weight distributionM w/M n = 1.12。
Embodiment 7: reaction solution C is used, continuously flowing prepares the own ester homopolymer of nine fluorine of methacrylic acid for illumination
By the own ester of nine fluorine of methacrylic acid: perfluor butyl iodide: bis- (4- the butyl phenyl) -10- phenyl -10H- pheno thiophenes of 3,7-
Piperazine=1000: 20: 1 molar ratio is by 5 mmol of above-mentioned raw materials, 0.1 mmol, 5 × 10-3Mmol is added separately to fill
Have in the bottle of magneton, 5 mL DMSO are added, reaction mixture is removed into oxygen after stirring and dissolving is uniform, is subsequently transferred to list
Member pump, it is 1.2 millimeters long by 3.2 for passing through internal diameter under the irradiation of 13 W white led lamps by reactant solution with the flow velocity of 50 μ L/min
The reaction microchannel of rice, exit obtains solution after reaction, passes through1It is 95% that H NMR, which measures monomer conversion, sample
With the mixing liquid precipitate for the first alcohol and water that volume ratio is 1: 1, it is dried under vacuum to constant weight, obtains white solid.GPC is measured poly-
Adduct molecule amountM n = 1.50 × 104G/mol and molecular weight distributionM w/M n = 1.08。
Embodiment 8: reaction solution C is used, continuously flowing prepares dodecafluorhe-ptylacrylate homopolymer for illumination
By dodecafluorhe-ptylacrylate: perfluor butyl iodide: bis- (4- the butyl phenyl) -10- phenyl -10H- phenthazine of 3,7-
=1000: 20: 1 molar ratio is by 5 mmol of above-mentioned raw materials, 0.1 mmol, 5 × 10-3Mmol is added separately to be equipped with
In the bottle of magneton, 5 mL DMF are added, reaction mixture is removed into oxygen after stirring and dissolving is uniform, is subsequently transferred to unit
Pump, with the flow velocity of 50 μ L/min by reactant solution under blue LED lamp irradiation by internal diameter for 1.2 millimeters long 3.2 meters anti-
Microchannel is answered, exit obtains solution after reaction, passes through1It is 96% that H NMR, which measures monomer conversion, sample volume
Than the mixing liquid precipitate of the first alcohol and water for 1: 1, it is dried under vacuum to constant weight, obtains white solid.The polymer that GPC is measured point
Son amountM n = 1.80 × 104G/mol and molecular weight distributionM w/M n = 1.14。
Second part: illumination continuous flow moves synthetic copolymer
Embodiment 9: reaction solution C is used, continuously flowing prepares the copolymer of hexafluorobutyl acrylate and methyl acrylate for illumination
By hexafluorobutyl acrylate: 4- cyano -4-(((hexyl is thio) thio carbonic acyl radical) thio) ethyl valerate: 3,7- is bis-
Phenthazine=1000 (4- butyl phenyl) -10- phenyl -10H-: 50: 1 molar ratio is by above-mentioned 5 mmol, 0.25
mmol、5 × 10-3Mmol is added separately in the bottle equipped with magneton, and 5 mL DMSO are added, will be anti-after stirring and dissolving is uniform
It answers mixture to remove oxygen, is subsequently transferred to modular pump 1；By methyl acrylate: bis- (4- the butyl phenyl) -10- phenyl-of 3,7-
Phenthazine=5000 10H-: 1 molar ratio is by above-mentioned 25 mmol, 5 × 10-3Mmol is added separately in bottle, is added
7 mL DMSO, remove oxygen for reaction mixture after stirring and dissolving is uniform, are subsequently transferred to modular pump 2；With 30 μ L/min's
Flow velocity is 1.2 millimeters long 3.3 meters of reaction microchannel by internal diameter under the irradiation of 13 W white led lamps by reactant solution,
First segment reacts the end access unit pump 2 of microchannel, equally with the flow velocity of 30 μ L/min by reactant methyl acrylate solution
Pass through second that internal diameter is 1.2 millimeters long 3.3 meters after solution mixing after reacting with first segment under the irradiation of 13 W white led lamps
Duan Fanying microchannel obtains solution after reaction in second segment reaction microchannel exit, passes through1H NMR measures propylene
The conversion ratio of sour hexafluoro butyl ester monomer is 97%, and the conversion ratio of methacrylate monomer is 99%, and sample volume ratio is 1: 1
The mixing liquid precipitate of first alcohol and water, is dried under vacuum to constant weight, obtains white solid.GPC measures first segment homopolymer polypropylene acid
The molecular weight of hexafluoro butyl esterM n = 5.20 × 103G/mol and molecular weight distributionM w/M nThe polymer that=1.04, GPC are measured
Molecular weightM n = 1.28 × 104G/mol and molecular weight distributionM w/M n = 1.07。
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (7)
1. a kind of method that continuous flow moves synthetic polymer, which is characterized in that synthesizer includes modular pump, transparent pipeline, adds
Heat or illumination apparatus and collection of products device；The step of specific synthesis, is as follows:
(1) reaction solution is prepared, is under stiring uniformly mixed each component, and removes the oxygen in reaction system；The reaction is molten
Liquid includes the following three types situation:Reaction solution A contains monomer, initiator, additive, solvent；Reaction solution B, contains
Monomer, initiator, catalyst, solvent；Reaction solution C contains monomer, initiator, photochemical catalyst, solvent；According to the molar ratio,
Monomer: initiator=1000: (1 ~ 100), used catalyst or photochemical catalyst are monomer dosage in reaction solution B and C
0.005~5 mol%；
(2) reaction mixture is transferred in modular pump, setting flow velocity is 5 ~ 500 μ L/min, and reaction mixture is allowed directly to add
Length of flow across is the pipe reaction container of 1.5 ~ 20 m under heat condition or under the illumination condition of different wave length, in collection device
It is middle to obtain corresponding reaction solution；
(3) by reaction solution purifying, processing, poly- (methyl) acrylate, poly- (methyl) fluoroalkyl acrylate, poly- third are obtained
Acrylamide and its derivative and one of polystyrene and its derivative.
2. the method according to claim 1, wherein additive is using azo as skeleton in the reaction solution A
Compound；Catalyst is the complex that copper or iron and nitrogen ligand are formed in the reaction solution B；Light in the reaction solution C
Catalyst be porphyrin, dihydrophenazine, phenoxazine, phenthazine be one or more of organic micromolecule compound of skeleton.
3. the method according to claim 1, wherein the reaction dissolvent be dimethyl sulfoxide,N, N- two
Methylformamide,N, NDimethyl acetamide,NOne of methyl pyrrolidone, acetonitrile are a variety of.
4. the method according to claim 1, wherein the initiator is alkyl halide, sulfocarbonate or complete
One of halothane test, shown in structure of initiator such as following formula (1), (2) or (3):
Wherein, in formula (1), R1For carbon atom number be 1 ~ 12 aliphatic group, aromatic group, the alkane that carbon atom number is 1 ~ 12
The dialkyl amido that the alkoxy, aryloxy group, carbon atom number that base sulfydryl, aryl thiol, carbon atom number are 1 ~ 12 are 1 ~ 12；R2For
Hydrogen atom, the alkyl that carbon atom number is 1 ~ 12；R3For carbon atom number be 1 ~ 12 alkyl, aryl；R4It is 1 ~ 12 for carbon atom number
Alkoxy carbonyl, the fluoroalkoxycarbonylgroups that carbon atom number is 1 ~ 12, aryloxycarbonyl, itrile group, the alkane that carbon atom number is 1 ~ 12
Base amino carbonyl；X is bromine or iodine；In formula (2), n is the integer between 0 ~ 12；In formula (3), R5For hydrogen, alkyl or aryl, R6For
Hydrogen, alkyl or aryl, R7For hydrogen, alkyl or aryl, X is Cl or Br atom.
5. method according to claim 1,2 or 4, which is characterized in that the monomer be selected from for (methyl) acrylate,
(methyl) fluoroalkyl acrylate, acrylamide and its derivative, Styrene and its derivatives, monomer structure such as following formula
(4) shown in ~ (6):
Wherein: in formula (4), R1For hydrogen atom or methyl, R2The aliphatic alkyl or hydroxy alkyl, virtue for being 1 ~ 18 for carbon atom number
Fragrant race's group；In formula (5), R3For hydrogen atom or methyl, R4For carbon atom number be 1 ~ 18 perfluoroalkyl or containing a small number of hydrogen atoms
Containing fluoroalkyl, n is 1 ~ 3 direct integer；In formula (6), R5The aliphatic alkyl for being 1 ~ 3 for hydrogen atom or carbon atom number, R6For hydrogen
The aliphatic alkyl that atom or carbon atom number are 1 ~ 3.
6. the method according to claim 1, wherein using directly heating or light when flowing polymerization in step (2)
According to two ways；The temperature range of reaction is heated in room temperature ~ 120 DEG C, illumination reaction is 390 ~ 700 nm's using launch wavelength
Light source, reaction mixture residence time and polymerization reaction time in flow channel are 0.5 ~ 10 hour.
7. according to claim 1, method described in 2,4 or 6, which is characterized in that in step (2), in first segment monomer polymerization knot
Shu Hou does not allow it to enter collection device, but enters second segment flowing reactive pipeline, terminates place's connection mixing in first segment pipeline
Connector accesses second modular pump, continues to react in pipe reaction container after being pumped into second segment monomer, in second segment pipe
Road reaction vessel exit obtains block copolymer.
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| CN114904573A (en) * | 2022-05-12 | 2022-08-16 | 南京先进生物材料与过程装备研究院有限公司 | Method for photoinduced modification of diaryl dihydrophenazine organic photocatalyst |
| CN115850543A (en) * | 2022-09-21 | 2023-03-28 | 青岛大学 | Methyl methacrylate anionic polymerization continuous polymerization process |
| CN116041606A (en) * | 2022-12-30 | 2023-05-02 | 东华大学 | Fluorine-containing acrylate polymer adhesive and preparation method and application thereof |
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| CN110354794A (en) * | 2019-07-04 | 2019-10-22 | 河南城建学院 | A kind of device and method that moving boundary polymerization continuously prepares polyaniline nano fiber |
| CN110354794B (en) * | 2019-07-04 | 2021-09-28 | 河南城建学院 | Device and method for continuously preparing polyaniline nanofibers through mobile interface polymerization |
| CN114904573A (en) * | 2022-05-12 | 2022-08-16 | 南京先进生物材料与过程装备研究院有限公司 | Method for photoinduced modification of diaryl dihydrophenazine organic photocatalyst |
| CN114904573B (en) * | 2022-05-12 | 2023-12-05 | 南京先进生物材料与过程装备研究院有限公司 | Method for photoinduction modification of diaryl dihydro phenazine organic photocatalyst |
| CN115850543A (en) * | 2022-09-21 | 2023-03-28 | 青岛大学 | Methyl methacrylate anionic polymerization continuous polymerization process |
| CN115850543B (en) * | 2022-09-21 | 2024-02-06 | 青岛大学 | Anionic polymerization continuous polymerization process for methyl methacrylate |
| CN116041606A (en) * | 2022-12-30 | 2023-05-02 | 东华大学 | Fluorine-containing acrylate polymer adhesive and preparation method and application thereof |
| CN116041606B (en) * | 2022-12-30 | 2024-02-27 | 东华大学 | Fluorine-containing acrylate polymer adhesive and preparation method and application thereof |
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