CN110156982A - A kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether - Google Patents
A kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether 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 Macroscopic single crystal fields, and in particular to a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether.The alkaline aqueous solution of phenol derivatives is squeezed into once-through type micro passage reaction respectively with aqueous oxidizing agent solution with metering pump and is preheated by the present invention, it is passed directly into again in enhancing mixed type continuous flow micro passage reaction afterwards, polyarylether solution is prepared through liquid liquid homogeneous reaction, is finally filtered, washed, is dried to obtain final product polyarylether.Operation of the present invention is simple, the safely controllable green of polymerization process, yield height and molecular weight distribution are relatively narrow, high production efficiency is, it can be achieved that continuity industrialized mass 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 homogeneous method 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.In addition, continuous flow micro passage reaction may be implemented
Multi-step successive reaction, just can directly amplify realization batch production without pilot scale, and highly-safe, production process is controllable, reaction choosing
Selecting property height.
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.
Road is both needed to consume a large amount of energy, be located by complicated operational sequence after solution polymerization process and precipitation polymerization method
All kinds of organic solvents such as reason, recycling toluene, methanol, high production cost, environmental pollution is serious, danger coefficient is high, this forces people
It goes to develop the polyphenylene oxide green synthesis method using water as single solvent, has achieved certain achievement.Japanese scholars Saito etc.
Using sodium hydroxide as pH adjusting agent, lauryl sodium sulfate be surfactant, potassium ferricyanate is oxidant, in full aqueous medium
The polyphenylene oxide (" German applied chemistry ", 2004,43 (6): 730-733) that molecular weight is 1.3 ten thousand has been prepared.It cares for into
Person is catalyst with magnetic loading type metallic ion-polyamide polyamide-amine complex compound, polyphenylene oxide prepared by full aqueous medium polymerization
Molecular weight has been further increased to 3.7 ten thousand (Chinese patent CN200910096196).Researcher is also constantly looking for, is attempting newly
Metal salt-amine complex compound catalyst, to constantly promoted selectivity, yield that phenol derivatives polymerize in full aqueous medium or
Molecular weight.Substantially, the synthesis of polyphenylene oxide is also the oxidative condensation polymerization realization by 2,6- xylenol, however so far
There has been no the research work reports for preparing polyphenylene oxide or polyarylether in full aqueous medium using continuous flow micro passage reaction, more
It is not able to achieve the complete industrialized large-scale production of aqueous medium method.
Summary of the invention
The object of the present invention is to provide a kind of liquid liquid homogeneous methods using continuous flow micro passage reaction synthesis polyarylether, and
In alkaline aqueous solution, phenol derivatives increases its solubility in water because generating corresponding salt, and after ensuring
Continuous reaction is mainly polymerize with the progress of C-O coupling mode, it is suppressed that the generation of by-product, improve the yield of polymer with
Selectivity.It is micro- logical that the alkaline aqueous solution of phenol derivatives and aqueous oxidizing agent solution with metering pump are squeezed into once-through type by the present invention respectively
Preheated in road reactor, after be passed directly into again enhancing mixed type continuous flow micro passage reaction in, through liquid liquid homogeneous reaction prepare
Polyarylether solution is obtained, is finally filtered, washed, is dried to obtain final product polyarylether.Operation of the present invention is simple, polymerization process
Safely controllable green, yield be high and molecular weight distribution is relatively narrow, high production efficiency is, it can be achieved that continuity industrialized mass production.This
Invention preparation condition is mild, production cost is low, be easy to mass and large-scale production, universality are strong, has good industrialization
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 homogeneous method of ether successively includes following operating procedure:
S1, with metering pump the alkaline aqueous solution of phenol derivatives and aqueous oxidizing agent solution are squeezed into once-through type microchannel plate respectively and answered
It is preheated in device, sets preheating temperature as 0 ~ 60 DEG C, the preheating residence time is 5 ~ 300s, and the preheating is controlled by external heat exchanger；
Phenol derivatives alkaline aqueous solution after S2, preheating is synchronous with aqueous oxidizing agent solution into continuous by N number of enhancing mixed type
It is reacted in the reaction module that stream micro passage reaction is composed in series, reaction temperature is equally controlled by external heat exchanger, and with
Preheating temperature is consistent, and polyarylether reaction mixture is flowed directly out from the outlet of the enhancing mixed type continuous flow micro passage reaction；
S3, the polyarylether reaction mixture flowed out from the enhancing mixed type continuous flow micro passage reaction is collected, stood to poly-
Aryl oxide product sufficiently settles, after using filter, wash and be dried to obtain final product polyarylether.
Further preferred technical solution is: in step S1, the phenol derivatives is in the alkaline aqueous solution
Concentration be 0.5 ~ 30wt%, preferred concentration be 2 ~ 20wt%, the alkaline aqueous solution pH > 7, preferred pH > 11, it is described
Also contain surfactant in alkaline aqueous solution, the surfactant is anionic surfactant, cation surface activating
One of agent and nonionic surface active agent, more preferably anionic surfactant, the use of the surfactant
Amount accounts for 0.01 ~ 3wt% of phenol derivatives.
Further preferred technical solution is: in step S1, the aqueous oxidizing agent solution is hydrogen peroxide or the potassium ferricyanide
One of aqueous solution, the concentration of the hydrogen peroxide are 1 ~ 50wt%, also contain metal salt-amine complex, institute in the hydrogen peroxide
0.1 ~ 45wt% that metal salt-amine complex accounts for phenol derivatives, more preferably 2 ~ 20wt% are stated, the potassium ferricyanide is water-soluble
The concentration of liquid is 1 ~ 50wt%.
Further preferred technical solution is: in step S1, the once-through type microchannel is the channel of tubular structure, institute
Flux of the alkaline aqueous solution of phenol derivatives in once-through type micro passage reaction is stated to control in 0.3 ~ 40mL/min, the benzene
Molar ratio between amphyl and the oxidant is 1:1.1 ~ 1:5.
Further preferred technical solution is: in step S2, the N between 1 ~ 20, preferred N be between 5 ~
Between 15, it is described enhancing mixed type continuous flow micro passage reaction in channel be heart-shaped structure, drops structure, T-type structure,
Spherical structure and spherical shape are with the mashed up of one or more of baffle arrangement, the alkaline aqueous solution of the phenol derivatives and oxidation
The total reaction time that agent aqueous solution stops in enhancing mixed type continuous flow micro passage reaction is 30 ~ 1800s.
Further preferred technical solution is: the constitutional repeating unit number in step S3, in the polyarylether strand
It is 6 ~ 200.
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.
Further preferred technical solution is: the metal salt be copper halide, 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
It is cuprous, and corresponding manganese salt and chromic salts, it can also be through copper, Cu oxide, manganese, Mn oxide, chromium, chromated oxide, copper
Or carbonate, copper or the manganese or the hydroxide of chromium of manganese or chromium and reacting between organic acid or inorganic acid, it is straight in hydrogen peroxide
Corresponding metal salt or its hydrate are delivered a child into, preferred metal salt is copper halide.
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- benzylmethylamine, N- benzyl -1- phenyl ethylamine, N, N- dimethyl
The mixture of one or more of butylamine, 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.
Further preferred technical solution is: heat transferring medium in the external heat exchanger be conduction oil, water, ice water,
One of brine ice and ethyl alcohol.
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 homogeneous method 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 3,4wt% 2,6 is configured, the sodium hydroxide of-xylenol is water-soluble
Liquid, pH value is controlled 11, and 0.75wt% lauryl sodium sulfate is added, and is slowly stirred uniformly；Add again into 20wt% hydrogen peroxide
Enter 1.2wt% copper-EDTA complex object, stirs evenly；By metering pump by 2,6, the sodium hydroxide of-xylenol
The straight trip channel module that aqueous solution and hydrogen peroxide squeeze into healthy and free from worry high-throughput micro passage reaction respectively is preheated, setting preheating temperature
Degree is 35 DEG C, the preheating residence time is 30s；2,6, the sodium hydrate aqueous solution of-xylenol is in straight trip channel module
Flux control is in 3mL/min, and 2,6, the H in-xylenol and hydrogen peroxide2O2Between molar ratio be 1:1.2.After preheating
2,6, the sodium hydrate aqueous solution and hydrogen peroxide of-xylenol are directly entered the healthy and free from worry high passes by 12 with cardioid channel
Amount micro passage reaction, which is composed in series in reaction module, carries out hybrid reaction, and reaction temperature is equally controlled to stop in 35 DEG C, reaction
Time is 1800s.The water dispersion solution for collecting the polyphenylene oxide flowed out from the outlet of healthy and free from worry cardioid channel module, 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 3700, PDI
=1.75。
Embodiment 2: as shown in attached drawing 1,2 and attached drawing 3, the sodium hydroxide for configuring 4wt% 2- methyl -6- bromophenol is water-soluble
Liquid, pH value is controlled 11, and 0.75wt% lauryl sodium sulfate is added, and is slowly stirred uniformly；Add again into 25wt% hydrogen peroxide
Enter 1.2wt% copper-EDTA complex object, stirs evenly；By metering pump by the sodium hydroxide of 2- methyl -6- bromophenol
The straight trip channel module that aqueous solution and hydrogen peroxide squeeze into healthy and free from worry high-throughput micro passage reaction respectively is preheated, setting preheating temperature
Degree is 45 DEG C, the preheating residence time is 40s；The sodium hydrate aqueous solution of 2- methyl -6- bromophenol is in straight trip channel module
Flux is controlled in 3mL/min, and the H in 2- methyl -6- bromophenol and hydrogen peroxide2O2Between molar ratio be 1:1.2.After preheating
2- methyl -6- bromophenol sodium hydrate aqueous solution and hydrogen peroxide be directly entered the healthy and free from worry high passes by 10 with cardioid channel
Amount micro passage reaction, which is composed in series in reaction module, carries out hybrid reaction, and reaction temperature is equally controlled to stop in 45 DEG C, reaction
Time is 1600s.The water dispersion solution for collecting the polyphenylene oxide flowed out from the outlet of healthy and free from worry cardioid channel module, 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 4200, PDI
=1.77。
Embodiment 3: as shown in attached drawing 1,2 and attached drawing 3,8wt% 2,6 is configured, the sodium hydroxide of-xylenol is water-soluble
Liquid, pH value is controlled 11, and 1.25wt% lauryl sodium sulfate is added, and is slowly stirred uniformly；Add again into 30wt% hydrogen peroxide
Enter 1.5wt% copper-EDTA complex object, stirs evenly；By metering pump by 2,6, the sodium hydroxide of-xylenol
The straight trip channel module that aqueous solution and hydrogen peroxide squeeze into healthy and free from worry high-throughput micro passage reaction respectively is preheated, setting preheating temperature
Degree is 45 DEG C, the preheating residence time is 40s；2,6, the sodium hydrate aqueous solution of-xylenol is in straight trip channel module
Flux control is in 2mL/min, and 2,6, the H in-xylenol and hydrogen peroxide2O2Between molar ratio be 1:1.2.After preheating
2,6, the sodium hydrate aqueous solution and hydrogen peroxide of-xylenol are directly entered the healthy and free from worry high passes by 17 with cardioid channel
Amount micro passage reaction, which is composed in series in reaction module, carries out hybrid reaction, and reaction temperature is equally controlled to stop in 45 DEG C, reaction
Time is 2700s.The water dispersion solution for collecting the polyphenylene oxide flowed out from the outlet of healthy and free from worry cardioid channel module, 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 4600, PDI
=1.70。
Embodiment 4: as shown in attached drawing 1,2 and attached drawing 3, configure 6wt% 2,3,6, the sodium hydroxide water of-pseudocuminol
Solution, pH value is controlled 11, and 1.0wt% lauryl sodium sulfate is added, and is slowly stirred uniformly；It is reconfigured the 35wt% potassium ferricyanide
Aqueous solution；By metering pump by 2,3,6, the sodium hydrate aqueous solution and potassium ferricyanide aqueous solution of-pseudocuminol are squeezed into respectively
The straight trip channel module of healthy and free from worry high throughput micro passage reaction is preheated, and setting preheating temperature is 35 DEG C, preheats the residence time
For 30s；2,3,6, flux of the sodium hydrate aqueous solution of-pseudocuminol in straight trip channel module is controlled in 3mL/min, and
2,3,6 ,-the molar ratio between pseudocuminol and the potassium ferricyanide is 1:2.1.2,3,6 after preheating, the hydrogen of-pseudocuminol
Aqueous solution of sodium oxide and hydrogen peroxide are directly entered the healthy and free from worry high-throughput micro passage reaction series connection group by 12 with cardioid channel
At hybrid reaction is carried out in reaction module, reaction temperature is equally controlled in 35 DEG C, reaction time 1800s.It collects from health
The water dispersion solution of the polyphenylene oxide flowed out in the outlet of calming heart type channel module washs and dry by filtering, methanol, obtains polyphenyl
Ether products.Number-average molecular weight by the polyphenyl ether products known to GPC test is 3900, PDI=1.69.
Embodiment 5: as shown in attached drawing 1,2 and attached drawing 3,10wt% 2,6, the sodium hydroxide water of-xylenol are configured
Solution, pH value is controlled 11.5, and 2.0wt% lauryl sodium sulfate is added, and is slowly stirred uniformly；It is reconfigured the cyaniding of 42wt% iron
Aqueous solutions of potassium；By metering pump by 2,6, the sodium hydrate aqueous solution and potassium ferricyanide aqueous solution of-xylenol are squeezed into respectively
The straight trip channel module of healthy and free from worry high throughput micro passage reaction is preheated, and setting preheating temperature is 48 DEG C, preheats the residence time
For 40s；2,6, the flux control of the sodium hydrate aqueous solution of-xylenol in straight trip channel module is in 2mL/min, and 2,
6 ,-the molar ratio between xylenol and the potassium ferricyanide is 1:2.1.2,6 after preheating, the sodium hydroxide of-xylenol
The healthy and free from worry high-throughput micro passage reaction that aqueous solution and hydrogen peroxide are directly entered by 17 with cardioid channel is composed in series reaction
Hybrid reaction is carried out in module, reaction temperature is equally controlled in 48 DEG C, reaction time 2700s.It collects from healthy and free from worry cardioid
The water dispersion solution of the polyphenylene oxide flowed out in channel module outlet washs and dry by filtering, methanol, obtains polyphenylene oxide production
Object.Number-average molecular weight by the polyphenyl ether products known to GPC test is 5300, PDI=1.83.
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. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether, it is characterised in that successively include following
Operating procedure:
S1, with metering pump the alkaline aqueous solution of phenol derivatives and aqueous oxidizing agent solution are squeezed into once-through type microchannel plate respectively and answered
It is preheated in device, sets preheating temperature as 0 ~ 60 DEG C, the preheating residence time is 5 ~ 300s, and the preheating is controlled by external heat exchanger；
Phenol derivatives alkaline aqueous solution after S2, preheating is synchronous with aqueous oxidizing agent solution into continuous by N number of enhancing mixed type
It is reacted in the reaction module that stream micro passage reaction is composed in series, reaction temperature is equally controlled by external heat exchanger, and with
Preheating temperature is consistent, and polyarylether reaction mixture is flowed directly out from the outlet of the enhancing mixed type continuous flow micro passage reaction；
S3, the polyarylether reaction mixture flowed out from the enhancing mixed type continuous flow micro passage reaction is collected, stood to poly-
Aryl oxide product sufficiently settles, after using filter, wash and be dried to obtain final product polyarylether.
2. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
Be characterized in that: in step S1, concentration of the phenol derivatives in the alkaline aqueous solution is 0.5 ~ 30wt%, the alkalinity
Aqueous solution pH > 7, surfactant is also contained in the alkaline aqueous solution, and the surfactant is anion surface active
One of agent, cationic surfactant and nonionic surface active agent, the dosage of the surfactant account for phenol and spread out
0.01 ~ 3wt% of biology.
3. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
Be characterized in that: in step S1, the aqueous oxidizing agent solution is one of hydrogen peroxide or potassium ferricyanide aqueous solution, the hydrogen peroxide
Concentration be 1 ~ 50wt%, metal salt-amine complex is also contained in the hydrogen peroxide, the metal salt-amine complex accounts for phenol and spreads out
0.1 ~ 45wt% of biology, the concentration of the potassium ferricyanide aqueous solution are 1 ~ 50wt%.
4. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
Be characterized in that: in step S1, the once-through type microchannel is the channel of tubular structure, the alkaline aqueous solution of the phenol derivatives
Flux in once-through type micro passage reaction controls between 0.3 ~ 40mL/min, the phenol derivatives and the oxidant
Molar ratio be 1:1.1 ~ 1:5.
5. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
It is characterized in that: in step S2, channel of the N between 1 ~ 20, in the enhancing mixed type continuous flow micro passage reaction
It is heart-shaped structure, drops structure, T-type structure, spherical structure and spherical shape with the mashed up of one or more of baffle arrangement, institute
What the alkaline aqueous solution and aqueous oxidizing agent solution for stating phenol derivatives stopped in enhancing mixed type continuous flow micro passage reaction
Total reaction time is 30 ~ 1800s.
6. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
Be characterized in that: in step S3, the constitutional repeating unit number in the polyarylether strand is 6 ~ 200.
7. a kind of liquid liquid homogeneous method 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.
8. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 3,
Be characterized in that: the metal salt be copper halide, 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 chromium
Salt can also be through the carbonate of copper, Cu oxide, manganese, Mn oxide, chromium, chromated oxide, copper or manganese or chromium, copper or manganese
Or the hydroxide of chromium and reacting between organic acid or inorganic acid, directly generated in hydrogen peroxide corresponding metal salt or its
Hydrate；The amine is dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, dibenzylamine, dicyclohexyl amine, diethanol amine, methyl ethylamine, N-
Methyl isopropylamine, N-methylcyclohexylamine, N- ethyl isopropylamine, N- benzylmethylamine, N- benzyl -1- phenyl ethylamine, N, N- dimethyl butyrate
The mixture of one or more of amine, N, N- Dialkylaminoethylamine and pyridine.
9. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
Be characterized in that: the channel waterpower in the once-through type micro passage reaction and enhancing mixed type continuous flow micro passage reaction is straight
Diameter is 0.5 ~ 10.0mm, and material is that glass, metal and its alloy, ceramics, monocrystalline silicon, surface are coated with the glass of erosion resistant coating, table
Face 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 of erosion resistant coating, fluorine-containing tree
One of rouge and high cross-linked thermal set type resin.
10. a kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether according to claim 1,
Be characterized in that: the heat transferring medium in the external heat exchanger is one of conduction oil, water, ice water, brine ice and ethyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718474A (en) * | 2020-08-04 | 2020-09-29 | 中国工程物理研究院激光聚变研究中心 | High-toughness high-modulus polymer and preparation method thereof |
| CN114736367A (en) * | 2022-04-24 | 2022-07-12 | 常州中英科技股份有限公司 | Green and safe polyarylether gas-liquid heterogeneous synthesis method |
| CN116199875A (en) * | 2023-01-19 | 2023-06-02 | 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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| CN116199875A (en) * | 2023-01-19 | 2023-06-02 | 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 |
| 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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