CN110156983A - Liquid-liquid heterogeneous method for synthesizing polyarylether by using continuous flow microchannel reactor - Google Patents
Liquid-liquid heterogeneous method for synthesizing polyarylether by using continuous flow microchannel reactor Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
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Abstract
The invention belongs to the field of polymer synthesis, and particularly relates to a liquid-liquid heterogeneous method for synthesizing polyarylether by using a continuous flow microchannel reactor. The method comprises the steps of taking organic solution of phenol derivatives and hydrogen peroxide as raw materials, taking a metal salt-amine complex as a catalyst, introducing the raw materials and the catalyst into a straight-flow type microchannel reactor by using a metering pump for preheating, directly introducing into an enhanced mixed type continuous flow microchannel reactor, carrying out liquid-liquid heterogeneous reaction to prepare a polyarylether solution, and finally carrying out precipitation, filtration, washing and drying to obtain a final product polyarylether. The method has the advantages of simple operation, safe and controllable polymerization process, high yield, narrow molecular weight distribution and high production efficiency, and can realize continuous industrial batch production.
Description
Technical field
The invention belongs to polymer synthesis techniques fields more particularly to a kind of synthesized using continuous flow micro passage reaction to gather
The liquid liquid multi-phases process of aryl oxide.
Background technique
Continuous flow micro passage reaction is a kind of small-sized reaction system, and line size is far smaller than conventional reactor,
The micromation of reaction channel can significantly increase the contact area between channel and heat transferring medium, improving heat exchanging efficiency.Microchannel
Interior extremely strong turbulent process may make mass transfer effect to have exponential growth, for out-phase reaction, mass transfer enhancing effect
Fruit becomes apparent.In addition, multi-step successive reaction may be implemented in continuous flow micro passage reaction, just can be directly amplified without pilot scale
Realize batch production, it is highly-safe, production process is controllable, reaction selectivity is high.
At this stage, continuous flow micro passage reaction is mainly used in the synthesis and its industrialized production of small molecule, phase
Comparatively, it is not that very much, major part is also only stopped in the synthesis of polymer industry and the research in modified field and report
Stay in laboratory stage.2004, Nagaki et al. reported cation of the vinyl butyl ether in microreactor for the first time
Polymerization reaction (" American Chemical Society ", 2004,126 (45): 14702-14703.).2005, Iwasaki et al. was micro-
In reactor by radical polymerization be prepared Mn=20800, PDI=3.16 butyl polyacrylate (" macromolecular ",
2005,38 (4): 1159-1163.).By 2008, Nagaki et al. realized in microreactor again the yin of styrene from
Sub- polymerization reaction (" macromolecular ", 2008,41 (17): 6322-6330.).In addition, polycondensation reaction equally can be in micro- reaction
It is carried out in system, for example, Kuboyama et al. is realized in micro- reaction system to diaminodiphenyl ether and m-phthaloyl chloride
Between polycondensation reaction (American Institute of Chemical Engineers (AIChE), 2005:132d.).
As the Typical Representative of polyarylether, polyphenylene oxide become the maximum resin of consumption figure in five large-engineering plastics it
One.Polyphenylene oxide has excellent electrical insulating property, dimensional stability, mechanical performance and high and low temperature resistance and extremely low dielectric damage
Consumption has been widely used in the fields such as auto industry, electronic apparatus industry, communications industry and mechanical industry.
Since nineteen sixty-five U.S. GE, company realized the industrialized production of polyphenylene oxide earliest, bulk polymerization has been developed
A variety of synthesizing means such as method, solution polymerization process, precipitation polymerization method and full aqueous medium polymerization.Wherein, mass polymerization still by
GE company releases earliest, although which avoids the use of solvent, but its reaction time is longer, the difficult control of polymerization process, separates and is stranded
Difficulty ultimately fails to realize industrialized production.Solution polymerization process is often using toluene, dimethylbenzene as solvent, and product is poly- at the end of reaction
Phenylate is still dissolved completely among solvent, and the rear poor solvent by polyphenylene oxide such as injection methanol is precipitated polyphenylene oxide, is heavy
It forms sediment.And in precipitation polymerization method, what organic solvent was selected is the mixed liquor of polyphenylene oxide good solvent and poor solvent, as polymerization is anti-
The progress answered, after the molecular weight of polyphenylene oxide increases to a certain extent, polyphenylene oxide is just precipitated from polymeric solution automatically, precipitates.
Nowadays, Sabic, Asahi Chemical Industry and Mitsubishi's gas are all made of solution polymerization process, and China's blue star chemical industry then uses precipitation polymerization method.Japan
Scholar Saito etc. using sodium hydroxide as pH adjusting agent, lauryl sodium sulfate is surfactant, potassium ferricyanate is oxidant,
Polyphenylene oxide (" German applied chemistry ", 2004,43 (6): 730- that molecular weight is 1.3 ten thousand have been prepared in full aqueous medium
733).Caring for into et al. and selecting magnetic loading type metallic ion-polyamide polyamide-amine complex compound is catalyst, and full aqueous medium is polymerize legal system
Standby polyphenylene oxide molecular weight has been further increased to 3.7 ten thousand.However, there has been no prepared using continuous flow micro passage reaction so far
The research work of polyphenylene oxide or polyarylether is reported.
Summary of the invention
The object of the present invention is to provide it is a kind of using continuous flow micro passage reaction synthesis polyarylether liquid liquid multi-phases process,
It is catalyst using the organic solution of phenol derivatives and hydrogen peroxide as raw material, metal salt-amine complex, with metering pump by each raw material
Pass first into once-through type micro passage reaction and preheat with catalyst, after be passed directly into again enhancing mixed type continuous flow microchannel plate
It answers in device, polyarylether solution is prepared through liquid liquid-liquid heterogeneous reaction, most precipitates, be filtered, washed, be dried to obtain through precipitation-afterwards
Final product polyarylether.Operation of the present invention is simple, polymerization process is safely controllable, yield is high and molecular weight distribution is relatively narrow, production effect
Rate height is, it can be achieved that continuity industrialized mass production.Preparation condition of the present invention is mild, production cost is low, is easy to mass and rule
Modelling production, universality are strong, have good industrialized production basis and wide application prospect.
The present invention solve the above problems the technical solution adopted is that: it is a kind of to synthesize poly- virtue using continuous flow micro passage reaction
The liquid liquid multi-phases process of ether successively includes following operating procedure:
S1, phenol derivatives and tri-n-octyl methyl ammonium chloride are added into catalyst solution, are reacted after being uniformly mixed
Liquid A；
S2, it the reaction solution A and hydrogen peroxide is passed through in once-through type micro passage reaction through metering pump respectively preheats, set
Preheating temperature is 0 ~ 60 DEG C, the preheating residence time is 5 ~ 300s, and the preheating is controlled by external heat exchanger；
It is carried out in reaction solution A entrance enhancing mixed type continuous flow micro passage reaction synchronous with hydrogen peroxide after S3, preheating
Reaction, reaction temperature are equally controlled by external heat exchanger and consistent with preheating temperature, and polymer product solution is from the reactor
Outlet flows directly out；
S4, the polyarylether reaction mixture flowed out from the enhancing mixed type continuous flow micro passage reaction is collected, to the poly- virtue
The poor solvent of polyarylether is added in ether products solution and stirs evenly rapidly, then stands sufficiently to be analysed to polyarylether product
Out, settle, after using filter, wash and be dried to obtain final product polyarylether, the repetitive structure in the polyarylether strand
Unit number is 6 ~ 120.
Further preferred technical solution is: in step S1, concentration of the phenol derivatives in the reaction solution A
For 3 ~ 48wt%, the dosage of the catalyst accounts for 0.1 ~ 45wt% of the phenol derivatives, more preferably 2 ~ 20wt%, described
The dosage of tri-n-octyl methyl ammonium chloride accounts for 0.005 ~ 0.3wt% of the phenol derivatives and catalyst total amount, more preferably
0.01~0.15wt%。
Further preferred technical solution is: in step S1, the solvent of the reaction solution A be can dissolve polyarylether,
Catalyst and tri-n-octyl methyl ammonium chloride but mixture with one or more of the immiscible organic solvent of water, including benzene,
Toluene, dimethylbenzene, chloroform, methylene chloride, dichloro-benzenes, nitrobenzene, aliphatic hydrocarbon and ether, more preferably benzene, toluene, diformazan
The aromatic hydrocarbons such as benzene, most preferably toluene.
Further preferred technical solution is: in step S2, the once-through type microchannel is the channel of tubular structure, institute
It states flux of the reaction solution A in the once-through type micro passage reaction and controls the phenol in 1 ~ 40mL/min, the reaction solution A
H in derivative and hydrogen peroxide2O2Between molar ratio be 1:1.01 ~ 1:3.
Further preferred technical solution is: in step S3, in the enhancing mixed type continuous flow micro passage reaction
Channel be heart-shaped structure, drops structure, T-type structure, spherical structure and spherical shape with one or more of baffle arrangement
It is mashed up, the reaction time that the reaction solution A and hydrogen peroxide stop in enhancing mixed type continuous flow micro passage reaction is 30 ~
600s。
Further preferred technical solution is that the phenol derivatives refers to the compound with following chemical structure
One or more of mixture:
Wherein R1, R2, R3 and R4 respectively independently represent H, alkyl, replace alkyl, aryl, substituted aryl and halogen atom, more excellent
Choosing is 2,6- xylenol, 2,6- diethyl phenol, 2,6- diη-propyl phenol, 2,6- diphenyl phenol, 2,6- diformazan
Phenylphenol, 2,3,6- pseudocuminol, 2- methyl -6- ethyl -phenol, 2- methyl -6- propylphenol, 2- ethyl -6- propylbenzene
Phenol, 2- ethyl -6- bromophenol, 2- methyl -6- tolyl phenol, 2- methyl -6- bromophenol and 2- ethyl -6- chlorophenol, it is optimal
Choosing is 2,6- xylenol.
Further preferred technical solution is: the catalyst is metal salt-amine complex, and the metal salt is halogenation
Copper, cuprous halide, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate, copper acetate, cuprous acetate, propionic acid copper, propionic acid be cuprous,
Dodecanoic acid copper, hexadecanoic acid copper, benzoic acid are cuprous, and corresponding manganese salt and chromic salts, can also be through copper, copper oxidation
The carbonate of object, manganese, Mn oxide, chromium, chromated oxide, copper or manganese or chromium, copper or manganese or chromium hydroxide and organic acid or
Reaction between inorganic acid directly generates corresponding metal salt or its hydrate in the reaction solution A, preferred to be catalyzed
Agent is cuprous halide；The amine is dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, dibenzylamine, dicyclohexyl amine, diethanol amine, first
Ethamine, N-methylisopropylamine, N-methylcyclohexylamine, N- ethyl isopropylamine, N- benzylmethylamine, N- benzyl -1- phenyl ethylamine, N, N- bis-
The mixture of one or more of methylbutylamine, N, N- Dialkylaminoethylamine and pyridine.
Further preferred technical solution is: the once-through type micro passage reaction and enhancing mixed type continuous flow are micro-
Channel hydraulic diameter in channel reactor is 0.5 ~ 10.0mm, material be glass, metal and its alloy, ceramics, monocrystalline silicon,
Surface is coated with the glass of erosion resistant coating, surface is coated with the metal of erosion resistant coating and its alloy, surface are coated with the ceramics of erosion resistant coating, surface applies
There are one of the monocrystalline silicon, fluorine resin and high cross-linked thermal set type resin of erosion resistant coating；Heat exchange in the external heat exchanger is situated between
Matter is one of conduction oil, water, ice water, brine ice and ethyl alcohol.
Further preferred technical solution is: in step S2, the concentration of the hydrogen peroxide is 1 ~ 50wt%.
Further preferred technical solution is: in step S4, the poor solvent of the polyarylether is methanol, second
The mixture of one or more of alcohol, isopropanol, butanol, acetone, butanone, methyl ethyl ketone, ether and ester, more preferably first
The alcohols such as alcohol, ethyl alcohol, isopropanol and butanol, most preferably methanol.
On the basis of above-mentioned technology path of the invention, it is living that surface can also be added into the reaction solution A or hydrogen peroxide
Property agent, the surfactant be anionic surfactant, cationic surfactant and nonionic surface active agent in
One or more of mixtures, the surfactant accounts for 0.01 ~ 3wt% of the phenol derivatives.
On the basis of above-mentioned technology path of the invention, hydrogen peroxide can be changed to potassium ferricyanide alkaline aqueous solution, at this time
It then need not be using catalyst, pH value > 7.0 of the potassium ferricyanide alkaline aqueous solution, preferably pH value > 9.0, more preferably
The molar ratio of pH value > 11.0, the potassium ferricyanide and phenol derivatives is 1:1 ~ 1:5.
Detailed description of the invention
Fig. 1 is operating procedure flow chart of the invention.
Fig. 2 is the structural schematic diagram of straight trip channel module in the present invention.
Fig. 3 is the structural schematic diagram of centre type micro passage reaction of the present invention.
Specific embodiment
The a kind of of offer that present invention be described in more detail by the following examples is closed using continuous flow micro passage reaction
At the liquid liquid multi-phases process of polyarylether.However, the embodiment is merely possible to provide explanation, rather than limit the present invention.
Embodiment 1: as shown in attached drawing 1,2 and attached drawing 3, by 0.37g CuBr, 5.24g N, N- di-n-butyl amine,
1.51g pyridine and 0.036g tri-n-octyl methyl ammonium chloride are dissolved in 100g toluene solution, and 80g 50wt% 2,6- is then added
Xylenol/toluene solution simultaneously stirs evenly rapidly, obtains reaction solution A.By metering pump by reaction solution A and 20wt% dioxygen
The straight trip channel module that water squeezes into healthy and free from worry high-throughput micro passage reaction respectively is preheated, and setting preheating temperature is 35 DEG C, in advance
The hot residence time is 30s；Flux of the reaction solution A in straight trip channel module controls 2, the 6- bis- in 4mL/min, reaction solution A
H in methylphenol and hydrogen peroxide2O2Between molar ratio be 1:1.2.Reaction solution A and 20wt% hydrogen peroxide after preheating directly connects
The cardioid channel module for entering healthy and free from worry high-throughput micro passage reaction carries out hybrid reaction, reaction temperature equally control 35 DEG C, instead
Answering the residence time is 420s.The toluene/water mixed solution of the polyphenylene oxide flowed out from the outlet of healthy and free from worry cardioid channel module is collected, this
The part Shi Huiyou polyphenylene oxide has been precipitated, further be added excessive methanol the polyphenylene oxide in toluene is sufficiently precipitated, after by
Filter, methanol washing and drying, obtain polyphenyl ether products.It is by the number-average molecular weight of the polyphenyl ether products known to GPC test
1600, PDI=1.85.
Embodiment 2: as shown in attached drawing 1,2 and attached drawing 3, by 0.38g CuBr, 5.32g N, N- di-n-butyl amine,
1.50g pyridine and 0.051g tri-n-octyl methyl ammonium chloride are dissolved in 100g toluene solution, and 80g 74wt% 2,3 is then added,
6- pseudocuminol/toluene solution simultaneously stirs evenly rapidly, obtains reaction solution A.It is by metering pump that reaction solution A and 30wt% is bis-
The straight trip channel module that oxygen water squeezes into healthy and free from worry high-throughput micro passage reaction respectively is preheated, setting preheating temperature is 40 DEG C,
The preheating residence time is 30s；Flux of the reaction solution A in straight trip channel module controls 2 in 3.5mL/min, reaction solution A,
H in 3,6- pseudocuminol and hydrogen peroxide2O2Between molar ratio be 1:1.3.Reaction solution A and 30wt% hydrogen peroxide after preheating
The cardioid channel module for being directly accessed healthy and free from worry high-throughput micro passage reaction carries out hybrid reaction, and reaction temperature is equally controlled 40
DEG C, reaction time 480s.The toluene/water mixing for collecting the polyphenylene oxide flowed out from the outlet of healthy and free from worry cardioid channel module is molten
Liquid has part polyphenylene oxide at this time and has been precipitated, be added excessive methanol the polyphenylene oxide in toluene is sufficiently precipitated, after by
Filter, methanol washing and drying, obtain polyphenyl ether products.It is by the number-average molecular weight of the polyphenyl ether products known to GPC test
2300, PDI=1.96.
Embodiment 3: as shown in attached drawing 1,2 and attached drawing 3, by 0.40g CuBr, 5.68g N, N- di-n-butyl amine,
1.62g pyridine and 0.073g tri-n-octyl methyl ammonium chloride are dissolved in 100g toluene solution, and 80g 78wt% 2,6- is then added
Xylenol/toluene solution simultaneously stirs evenly rapidly, obtains reaction solution A.By metering pump by reaction solution A and 30wt% dioxygen
The straight trip channel module that water squeezes into healthy and free from worry high-throughput micro passage reaction respectively is preheated, and setting preheating temperature is 45 DEG C, in advance
The hot residence time is 40s；Flux of the reaction solution A in straight trip channel module controls 2,6- in 3.5mL/min, reaction solution A
H in xylenol and hydrogen peroxide2O2Between molar ratio be 1:1.3.Reaction solution A and 30wt% hydrogen peroxide after preheating is direct
The cardioid channel module for accessing healthy and free from worry high-throughput micro passage reaction carries out hybrid reaction, reaction temperature equally control 45 DEG C,
Reaction time is 480s.The toluene/water mixed solution of the polyphenylene oxide flowed out from the outlet of healthy and free from worry cardioid channel module is collected,
Part polyphenylene oxide is had at this time to be precipitated, and excessive methanol is added, the polyphenylene oxide in toluene is sufficiently precipitated, by filtering, first
Alcohol washing and drying, obtain polyphenyl ether products.Number-average molecular weight by the polyphenyl ether products known to GPC test is 3100, PDI
=2.25。
Embodiment 4: as shown in attached drawing 1,2 and attached drawing 3,47% HBr solution of 0.27g and 0.051g Cu2O are dissolved in
Contain 0.12g N, N '-di-t-butyl ethylenediamine, 1.51g pyridine, 0.60g N, N '-di-n-butyl amine and 0.036g trioctylphosphine
In the 100g toluene solution of ammonio methacrylate, subsequent addition 80g 50wt% 2- methyl -6- bromophenol/toluene solution is simultaneously rapid
It stirs evenly, obtains reaction solution A.Reaction solution A and 20wt% hydrogen peroxide are squeezed into healthy and free from worry high-throughput microchannel respectively by metering pump
The straight trip channel module of reactor is preheated, and setting preheating temperature is 35 DEG C, the preheating residence time is 30s；Reaction solution A is straight
H of the flux control in the 2- methyl -6- bromophenol and hydrogen peroxide in 40mL/min, reaction solution A in row of channels module2O2It
Between molar ratio be 1:1.2.Reaction solution A and 20wt% hydrogen peroxide after preheating is directly accessed healthy and free from worry high-throughput micro passage reaction
Cardioid channel module carry out hybrid reaction, reaction temperature equally controls in 35 DEG C, reaction time 420s.It collects from health
The toluene/water mixed solution of the polyphenylene oxide flowed out in the outlet of calming heart type channel module, has part polyphenylene oxide at this time and has been precipitated,
Excessive methanol, which is added, is precipitated the polyphenylene oxide in toluene sufficiently, washs by filtering, methanol and dry, obtains polyphenylene oxide production
Object.Number-average molecular weight by the polyphenyl ether products known to GPC test is 1800, PDI=1.93.
Embodiment 5: as shown in attached drawing 1,2 and attached drawing 3,47% HBr solution of 0.30g and 0.055g Cu2O are dissolved in
Contain 0.13g N, N '-di-t-butyl ethylenediamine, 1.55g pyridine, 0.65g N, N '-di-n-butyl amine and 0.08g trioctylphosphine
In the 100g toluene solution of ammonio methacrylate, 90g 70wt% 2 is then added, 6- xylenol/toluene solution simultaneously stirs rapidly
It mixes uniformly, obtains reaction solution A.Reaction solution A and 30wt% hydrogen peroxide are squeezed into healthy and free from worry high-throughput microchannel plate respectively by metering pump
The straight trip channel module of device is answered to be preheated, setting preheating temperature is 45 DEG C, the preheating residence time is 35s；Reaction solution A is keeping straight on
H of the flux control in 2, the 6- xylenol and hydrogen peroxide in 3mL/min, reaction solution A in channel module2O2Between
Molar ratio is 1:1.3.Reaction solution A and 30wt% hydrogen peroxide after preheating is directly accessed the heart of healthy and free from worry high-throughput micro passage reaction
Type channel module carries out hybrid reaction, and reaction temperature is equally controlled in 45 DEG C, reaction time 540s.It collects from the healthy and free from worry heart
The toluene/water mixed solution of the polyphenylene oxide flowed out in the outlet of type channel module, has part polyphenylene oxide at this time and has been precipitated, and is added
The polyphenylene oxide in toluene is precipitated sufficiently in excessive methanol, washs and dry by filtering, methanol, obtains polyphenyl ether products.It is logical
The number-average molecular weight for crossing the polyphenyl ether products known to GPC test is 2700, PDI=2.11.
Embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned embodiment party
Formula within the scope of knowledge possessed by those of ordinary skill in the art can also be before not departing from present inventive concept
It puts and makes various modifications.These be all without creative modification, as long as in scope of the presently claimed invention all by
To the protection of Patent Law.
Claims (10)
1. it is a kind of using continuous flow micro passage reaction synthesis polyarylether liquid liquid multi-phases process, it is characterised in that successively include with
Lower operating procedure:
S1, phenol derivatives and tri-n-octyl methyl ammonium chloride are added into catalyst solution, are reacted after being uniformly mixed
Liquid A；
S2, it the reaction solution A and hydrogen peroxide is passed through in once-through type micro passage reaction through metering pump respectively preheats, set
Preheating temperature is 0 ~ 60 DEG C, the preheating residence time is 5 ~ 300s, and the preheating is controlled by external heat exchanger；
It is carried out in reaction solution A entrance enhancing mixed type continuous flow micro passage reaction synchronous with hydrogen peroxide after S3, preheating
Reaction, reaction temperature are equally controlled by external heat exchanger and consistent with preheating temperature, and polymer product solution is from the reactor
Outlet flows directly out；
S4, the polyarylether reaction mixture flowed out from the enhancing mixed type continuous flow micro passage reaction is collected, to the poly- virtue
The poor solvent of polyarylether is added in ether products solution and stirs evenly rapidly, then stands sufficiently to be analysed to polyarylether product
Out, settle, after using filter, wash and be dried to obtain final product polyarylether, the repetitive structure in the polyarylether strand
Unit number is 6 ~ 120.
2. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: concentration of the phenol derivatives in the reaction solution A is 3 ~ 48wt%, the catalyst in step S1
Dosage accounts for 0.1 ~ 45wt% of the phenol derivatives, the dosage of the tri-n-octyl methyl ammonium chloride account for the phenol derivatives and
0.005 ~ 0.3wt% of catalyst total amount.
3. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the solvent of the reaction solution A is that can dissolve polyarylether, catalyst and tricaprylmethyl chlorination in step S1
Ammonium but mixture with one or more of the immiscible organic solvent of water, including benzene,toluene,xylene, chloroform, dichloro
Methane, dichloro-benzenes, nitrobenzene, aliphatic hydrocarbon and ether.
4. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the once-through type microchannel is the channel of tubular structure, and the reaction solution A is in the once-through type in step S2
Flux in micro passage reaction controls the H in the phenol derivatives and hydrogen peroxide in 1 ~ 40mL/min, the reaction solution A2O2
Between molar ratio be 1:1.01 ~ 1:3.
5. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the channel in the enhancing mixed type continuous flow micro passage reaction is heart-shaped structure, drops in step S3
Structure, T-type structure, spherical structure and spherical shape are with the mashed up of one or more of baffle arrangement, the reaction solution A and hydrogen peroxide
The reaction time stopped in enhancing mixed type continuous flow micro passage reaction is 30 ~ 600s.
6. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized in that the phenol derivatives refers to the mixture of one or more of compound with following chemical structure:
Wherein R1, R2, R3 and R4 respectively independently represent H, alkyl, replace alkyl, aryl, substituted aryl and halogen atom.
7. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the catalyst is metal salt-amine complex, the metal salt is copper halide, cuprous halide, copper sulphate, sulphur
The cuprous, copper nitrate of acid, cuprous nitrate, copper acetate, cuprous acetate, propionic acid copper, propionic acid be cuprous, dodecanoic acid copper, hexadecanoic acid copper,
Benzoic acid is cuprous, and corresponding manganese salt and chromic salts, can also be through copper, Cu oxide, manganese, Mn oxide, chromium, chromium oxidation
The carbonate of object, copper or manganese or chromium, copper or manganese or the hydroxide of chromium and reacting between organic acid or inorganic acid, described anti-
It answers and directly generates corresponding metal salt or its hydrate in liquid A；The amine be dimethylamine, diethylamine, di-n-propylamine, dibutyl amine,
Dibenzylamine, dicyclohexyl amine, diethanol amine, methyl ethylamine, N-methylisopropylamine, N-methylcyclohexylamine, N- ethyl isopropylamine, N- benzyl
One or more of methylamine, N- benzyl -1- phenyl ethylamine, N, N- dimethyl butylamine, N, N- Dialkylaminoethylamine and pyridine mix
Close object.
8. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the channel waterpower in the once-through type micro passage reaction and enhancing mixed type continuous flow micro passage reaction
Diameter is 0.5 ~ 10.0mm, material be glass, metal and its alloy, ceramics, monocrystalline silicon, surface be coated with erosion resistant coating glass,
Surface is coated with the metal of erosion resistant coating and its alloy, surface are coated with the ceramics of erosion resistant coating, surface is coated with the monocrystalline silicon, fluorine-containing of erosion resistant coating
One of resin and high cross-linked thermal set type resin；Heat transferring medium in the external heat exchanger is conduction oil, water, ice water, ice
One of salt water and ethyl alcohol.
9. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the concentration of the hydrogen peroxide is 1 ~ 50wt% in step S2.
10. a kind of liquid liquid multi-phases process using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized by: the poor solvent of the polyarylether is methanol, ethyl alcohol, isopropanol, butanol, acetone, fourth in step S4
The mixture of one or more of ketone, methyl ethyl ketone, ether and ester.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617711A (en) * | 2020-06-15 | 2020-09-04 | 辽宁石化职业技术学院 | Microreactor and diarylethane preparation method based on microreactor |
| CN114249894A (en) * | 2021-11-29 | 2022-03-29 | 四川大学 | Ether-containing polymer containing active group and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111617711A (en) * | 2020-06-15 | 2020-09-04 | 辽宁石化职业技术学院 | Microreactor and diarylethane preparation method based on microreactor |
| CN114249894A (en) * | 2021-11-29 | 2022-03-29 | 四川大学 | Ether-containing polymer containing active group and preparation method and application thereof |
| CN114716666A (en) * | 2022-04-24 | 2022-07-08 | 常州中英科技股份有限公司 | Polyarylether synthesis method based on gas-liquid heterogeneous phase method and continuous flow microchannel reactor |
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| CN116199875B (en) * | 2023-01-19 | 2023-11-17 | 北京中油创宇科技有限公司 | Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor |
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