CN219323870U

CN219323870U - Precipitation device and production system of polyphenyl ether

Info

Publication number: CN219323870U
Application number: CN202320113400.8U
Authority: CN
Inventors: 魏小林; 杨磊; 邵晶晶
Original assignee: CHINA NATIONAL CHEMICAL ENGINEERING CO LTD; China Chemical Technology Research Institute
Current assignee: CHINA NATIONAL CHEMICAL ENGINEERING CO LTD; China Chemical Technology Research Institute
Priority date: 2023-01-19
Filing date: 2023-01-19
Publication date: 2023-07-11
Anticipated expiration: 2033-01-19

Abstract

The utility model provides a device and a system for separating out polyphenyl ether. The separating out device comprises a concentrating mixer, a toluene condenser, a toluene collecting tank and a slurry pump; the top of the concentrating mixer comprises a poor solvent inlet and a toluene outlet, and the bottom comprises a slurry outlet; the toluene outlet is sequentially connected with the toluene condenser and the toluene collecting tank, and the slurry outlet is connected with the slurry pump; a stirring device is arranged in the concentrating mixer; the concentrating mixer is also provided with a heating device. The production system adopts the solution polymerization and coupling method to prepare the polyphenyl ether, especially the low molecular weight polyphenyl ether, has adjustable molecular weight, can be controlled more precisely, has narrow molecular weight dispersibility and short process flow. The post-treatment adopts a unique precipitation device integrating concentration and mixing to precipitate the polymer solution, the use amount of poor solvent is greatly reduced, and the yield of the polymer is high.

Description

Precipitation device and production system of polyphenyl ether

Technical Field

The utility model belongs to the field of polyphenyl ether preparation, and particularly relates to a polyphenyl ether precipitation device and a production system, in particular to a low molecular weight polyphenyl ether precipitation device and a production system.

Background

The polyphenyl ether is a thermoplastic engineering plastic, has excellent comprehensive performance, is mainly characterized by heat resistance, water absorption resistance and good dimensional stability, particularly has extremely low dielectric constant and dielectric loss in a wider frequency range, and is one of ideal materials for manufacturing high-frequency and high-speed copper-clad plates.

The polyphenyl ether resin is one of five general engineering plastics, has good mechanical property, electrical insulation property, heat resistance, flame retardance, water resistance, chemical stability and the like, and becomes a preferred resin matrix of the high-performance copper-clad plate substrate material. Because the molecular weight of the general polyphenyl ether is too high, in actual use, the general polyphenyl ether has large melt viscosity, poor fluidity and poor compatibility with other resins, so that the general polyphenyl ether is limited to a certain extent in the application of copper-clad plates. In order to make the polyphenyl ether have better application in the field of high-performance copper-clad plates, the molecular weight of the polymer must be reduced, and hydroxyl groups are introduced at two ends of the polymer molecule, so that the obtained double-end hydroxyl low-molecular-weight polyphenyl ether not only has the excellent characteristics of general high-molecular-weight polyphenyl ether, but also has excellent solubility in toluene and methyl ethyl ketone, and the hydroxyl groups at two ends of the polyphenyl ether have very high reactivity, so that the fluidity and compatibility of the polyphenyl ether can be further improved, and the polyphenyl ether can be better applied to the field of high-performance copper-clad plates.

The synthesis method of the low molecular weight dihydroxy polyphenyl ether can be categorized into three methods: the first is a coupling method, such as coupling of low molecular weight monohydroxy polyphenylene ether with 3, 5-tetramethylbiphenyl di (TMDPQ); the second method is copolymerization of monomers with diphenol coupling agents, such as bisphenol A or tetramethyl bisphenol A; the third method is to directly prepare the high molecular weight polyphenyl ether by a redistribution method. The first coupling method is to prepare low molecular weight polyphenyl ether and then react with TMDPQ, and the route is longer. The second and third methods are more studied, and the defects of the methods are that the single-functionality polyphenyl ether is formed by the homopolymer of xylenol monomer during the copolymerization, so that the product is impure. Redistribution, while producing a difunctional polyphenylene ether, gives a polymer having a non-uniform molecular weight, a large and uncontrollable molecular weight dispersion, resulting in a significant decrease in the solubility of the polymer.

In the preparation of low molecular weight polyphenylene ethers, in order to more precisely control the molecular weight and molecular weight distribution thereof, solution polymerization is generally carried out using a good solvent such as toluene. The conventional method for precipitating polyphenylene ether from a polymer solution is to add a poor solvent methanol to the polymer solution to precipitate the polymer. However, the solubility of low molecular weight polyphenylene ethers in toluene reaches 50% at room temperature. Therefore, the conventional precipitation method of common polyphenyl ether needs to adopt a very large amount of poor solvent, the yield of the polymer is very low, and part of polymer molecules are dissolved in a mixed solution of toluene and methanol and cannot be precipitated.

CN202110943158.2 discloses a preparation method of one-pot low molecular weight double-end hydroxyl polyphenyl ether. A good solvent is adopted, a phenol monomer and a catalyst are added, a polyphenyl ether homopolymer intermediate is prepared under the condition of oxygen introduction, and then an inorganic acid catalyst and acetone are added for condensation coupling reaction. And then pouring the reaction solution into 30 times of the volume of the reaction solution to separate out the poor solvent, wherein the use amount of the poor solvent used for preparing the unit polymer is large. The following index is given for only one batch of polymer in this patent: the molecular weight (2536), dispersity (1.784), and the index of hydroxyl functionality are not shown, and it is very challenging to react both homopolymer intermediates with acetone to form a double-ended hydroxyl polymer during the recondensing reaction due to mass transfer.

CN201410503838.2 discloses a preparation method of multifunctional agglomerated phenyl ether resin, which mainly utilizes redistribution of common polyphenyl ether resin to prepare low molecular weight polyphenyl ether, uses a large amount of peroxide initiator and phase transfer catalyst in the reaction process, and has complex post-treatment procedures, thus being not used for industrial production.

The system for producing the polyphenyl ether adopts toluene as a solvent, prepares the low molecular weight polyphenyl ether by a solution coupling method, transfers the low molecular weight polyphenyl ether into a concentrating mixer for treatment, and can obtain the low molecular weight dihydroxy polyphenyl ether solid powder with high yield after filtration and drying.

Disclosure of Invention

The utility model aims to provide a polyphenylene ether precipitation device and a production system, in particular to a polyphenylene ether precipitation device and a production system which are applicable to low molecular weight polyphenylene ether. The production system comprising the precipitation device is short in technological reaction flow, simple to operate, safe and easily available in raw materials, easy to industrialize in polymer precipitation, high in yield, capable of effectively improving the yield and capable of accurately controlling the molecular weight and molecular weight polydispersity of the polymer.

In order to achieve the above purpose, the present utility model adopts the following technical scheme:

the utility model provides a polyphenyl ether precipitation device, which comprises a concentrating mixer, a toluene condenser, a toluene collecting tank and a slurry pump;

the top of the concentrating mixer comprises a poor solvent inlet and a toluene outlet, and the bottom comprises a slurry outlet; the toluene outlet is sequentially connected with the toluene condenser and the toluene collecting tank, and the slurry outlet is connected with the slurry pump;

a stirring device is arranged in the concentrating mixer; the concentrating mixer is also provided with a heating device.

And after the reaction preparation unit adopts toluene as a solvent and the solution coupling method is adopted to prepare the polyphenyl ether, transferring the obtained polymer solution containing the polyphenyl ether into the concentrating mixer for treatment. Under the heating of a heating device, the good solvent toluene in the heating device is distilled out of the system to obtain viscous polymer fluid; and adding a poor solvent to precipitate polyphenyl ether, mixing the materials under the stirring action of a stirring device to form a suspension of the polymer in the poor solvent, and outputting the suspension from a slurry outlet for filtering and drying to obtain the dihydroxyl polyphenyl ether solid powder with high yield.

According to the precipitation device of the present utility model, preferably, the stirring device includes a motor, a transmission main shaft, and a double-layer helical blade disposed on the transmission main shaft.

According to the precipitation device of the present utility model, preferably, the spiral conveying direction of the inner spiral blade of the double-layer spiral blade is outward, and the spiral conveying direction of the outer spiral blade is inward. Both inward and outward are the drive spindles.

The inner and outer helical blades of the stirring device on the transmission main shaft drive the material in the barrel body, so that the stirring device turns the material in the barrel body in a large range. When the concentrating mixer works, the inner helical blades drive the materials close to the axle center to rotate at the axle center, the materials are axially pushed from inside to outside to be conveyed, the outer helical blades drive the materials close to the barrel wall to rotate at the axle center, the materials are axially pushed from both sides to inside to be gathered, and the materials can be powdered to form uniform suspension in a short time. The materials form a low-power and high-efficiency mixed environment under the convection motion of the double-layer helical blades.

According to the precipitation device of the present utility model, preferably, the stirring device further comprises a frame stirring structure disposed on the transmission main shaft, and a distance between an outer edge of the frame stirring structure and an inner wall of the concentrating mixer is 0 to 50mm. The frame type stirring structure can play a role of a scraper, and materials adhered to the inner wall of the concentrating mixer are cleaned and continuously mixed under the action of the double-layer helical blades.

More preferably, the distance between the outer edge of the frame-type stirring structure and the inner wall of the concentrating mixer is 0-20 mm.

According to the precipitation device of the present utility model, preferably, the main body of the concentrating mixer is a cylinder, and the lower part is a cone.

According to the precipitation device of the present utility model, preferably, the heating device includes a jacket disposed outside the concentrating mixer, the top of the jacket includes a hot fluid inlet, and the bottom of the jacket includes a cold fluid outlet. Specifically, the hot fluid input by the hot fluid inlet can be hot water or heat conduction oil, the hot fluid heats the materials in the concentrating mixer to 40-60 ℃ under a certain negative pressure, so that toluene in the materials is evaporated and output from the toluene outlet, and the fluid after heat exchange is output from the cold fluid outlet to the jacket, and the corresponding fluid can be cold water or cold heat conduction oil.

According to the precipitation device of the present utility model, preferably, a vacuum pump is connected to the top of the toluene collection tank for creating a negative pressure condition to reduce the temperature at which toluene evaporates.

According to the precipitation device, preferably, the bottom of the toluene collection tank is connected with a toluene conveying pump, and toluene can be conveyed to the reaction preparation device for recycling.

According to the precipitation apparatus of the present utility model, preferably, the precipitation apparatus further includes a poor solvent tank and a poor solvent metering pump, and the poor solvent tank is connected to the poor solvent metering pump and the poor solvent inlet in order, for adding a poor solvent, such as methanol, into the concentrating mixer.

According to the precipitation device of the present utility model, preferably, the precipitation device further includes a filtering device and a drying device, and the slurry pump is sequentially connected to the filtering device and the drying device, for filtering the slurry outputted and drying the solids separated by the filtering.

In another aspect, the utility model provides a system for producing polyphenylene ether, comprising a reaction preparation device and the precipitation device. And each raw material in the reaction preparation device reacts to generate the polyphenyl ether.

The specific process flow for producing the polyphenyl ether by using the production system comprises the following steps:

the first step: under the action of a catalyst, introducing oxygen into a phenolic monomer such as 2, 6-xylenol to prepare a monohydroxy polyphenyl ether homopolymer, water and 3, 5-tetramethyl biphenyl biquinone, wherein the reaction process is shown in the following reaction formula:

and a second step of: and (3) performing condensation reaction on the monohydroxy polyphenyl ether homopolymer and diphenol monomers to prepare the dihydroxyl polyphenyl ether polymer. The diphenol monomer is aromatic quinone or aromatic diphenol. The reaction process is shown in the following reaction formula:

wherein X: diphenol monomers such as bisphenol A, bisphenol F, tetramethyl bisphenol A, tetramethyl diphenoquinone, and the like.

And a third step of: and (3) transferring the polymer solution containing the polyphenyl ether obtained in the second step into the precipitation device for post treatment to obtain the solid powder of the dihydroxyl polyphenyl ether.

The reaction conditions of the first step can be specifically: adding a certain amount of phenolic monomers, good solvents toluene and copper amine catalysts into a reaction kettle provided with condensation reflux, gas bubbling and stirring, and reacting for 0.5-3 h under the condition of 5-50 ℃ under the condition of oxygen introduction to obtain the monohydroxy polyphenyl ether polymer solution.

Preferably, the content of the phenolic monomer in the good solvent is 8% -30%, the molar ratio of the phenolic monomer to oxygen is 0.2:1-10:1, and the reaction is applicable to 1-4 methyl substituted phenolic monomers.

Preferably, in the copper amine catalyst, copper may be a halogen-containing copper salt such as copper chloride, cuprous chloride, copper bromide, or cuprous bromide, and the amine may be monoamine containing 2 to 4 carbon atoms, diamine, or a mixture thereof, or monoamine containing 2 to 4 carbon atoms substituted with 1 to 4 carbon atoms, diamine, or a mixture thereof, and the addition amount of the copper amine catalyst is 0.1 to 6% with respect to 1mol of the reactant phenolic monomer.

The reaction conditions of the second step can be specifically: and (3) respectively adding diphenol monomers and acid catalysts into the reaction liquid obtained in the first step of reaction, and reacting for 0.5-4 hours at the temperature of 10-80 ℃ to obtain the double-end hydroxyl polyphenyl ether polymer solution.

Preferably, the acid catalyst may be a conventional strong acid catalyst such as concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid, etc., the type of which is not limited. The added diphenol monomer may be a chemical substance containing a dihydroxy group such as bisphenol a, bisphenol F, tetramethyl bisphenol a, tetramethyl diphenyl biquinone, etc., and the addition amount of the acid catalyst is 0.1 to 2% relative to 1mol of diphenol substance.

Preferably, the addition amount of the diphenol monomer is 5 to 30 percent (mass ratio) of the monohydroxy polyphenyl ether homopolymer in the first-step polymer solution.

The third step specifically comprises: and after the second step of reaction is finished, adding the obtained polymer solution into a concentrating mixer, heating the polymer solution by a heating device, evaporating the good solvent toluene under a certain negative pressure condition to obtain viscous polymer fluid, and controlling the evaporation amount of the good solvent to control the viscous liquid to have certain fluidity. And when the temperature is reduced to 30-50 ℃, adding a poor solvent with the polymer amount being 2-6 times, stirring for 0.5-4 h to obtain a highly dispersed polymer particle suspension, outputting the suspension from a slurry outlet, filtering, and drying to obtain the double-end hydroxyl polyphenyl ether powder.

Preferably, the content of the good solvent in the obtained viscous polymer fluid is 10-20% (mass ratio), and the poor solvent added is monohydric alcohol of C1-C4, preferably methanol; the addition amount of the poor solvent is 2 to 6 times, preferably 2 to 4 times, the amount of the polymer.

The production system of the utility model adopts the solution polymerization and coupling method to prepare the polyphenyl ether, especially the low molecular weight polyphenyl ether, has adjustable molecular weight and can be controlled more precisely, has narrow molecular weight dispersibility and short process flow. The post-treatment adopts a unique precipitation device integrating concentration and mixing to precipitate the polymer solution, the use amount of poor solvent is greatly reduced, and the yield of the polymer is high.

Drawings

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way. In addition, the shapes, proportional sizes, and the like of the respective components in the drawings are merely illustrative for aiding in understanding the present utility model, and are not particularly limited. Those skilled in the art with access to the teachings of the present utility model can select a variety of possible shapes and scale sizes to practice the present utility model as the case may be.

FIG. 1 is a schematic view showing a precipitation apparatus for polyphenylene ether in a preferred embodiment of the present utility model.

Fig. 2 is a schematic diagram showing a preferred structure of the concentrating mixer in the precipitation apparatus of fig. 1.

FIG. 3 is a nuclear magnetic resonance spectrum of the product obtained in application example 1.

Reference numerals illustrate:

1. the device comprises a concentrating mixer, 2, a toluene condenser, 3, a toluene collecting tank, 4, a slurry pump, 5, a vacuum pump, 6, a toluene conveying pump, 7, a poor solvent storage tank, 8 and a poor solvent metering pump;

11. poor solvent inlet, 12, toluene outlet, 13, slurry outlet, 14, stirring device, 15, motor, 16, transmission main shaft, 17, double-layer helical blade, 18, frame stirring structure, 19, jacket, 19-1, hot fluid inlet, 19-2, cold fluid outlet.

Detailed Description

In order to more clearly illustrate the present utility model, the present utility model will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this utility model is not limited to the details given herein.

In addition, some terms mentioned in the embodiments of the present utility model, such as "top", "bottom", "lower", etc., have meanings related to the placement of the device, and should not be construed as limiting the scope of the present utility model.

The utility model firstly provides a polyphenyl ether precipitation device, as shown in figure 1, which comprises a concentrating mixer 1, a toluene condenser 2, a toluene collecting tank 3 and a slurry pump 4;

the top of the concentrating mixer 1 comprises a poor solvent inlet 11 and a toluene outlet 12, and the bottom comprises a slurry outlet 13; the toluene outlet 12 is sequentially connected with the toluene condenser 2 and the toluene collection tank 3, and the slurry outlet 13 is connected with the slurry pump 4; a stirring device 14 is arranged in the concentrating mixer 1; the concentrating mixer is also provided with a heating device.

After preparing polyphenylene ether by a solution coupling method using toluene as a solvent, the obtained polymer solution was transferred to the concentrating mixer 1 for treatment. Under the heating of a heating device, the good solvent toluene in the heating device is distilled out of the system to obtain viscous polymer fluid; the poor solvent is added to the slurry to separate out the polyphenyl ether, the materials are mixed under the stirring action of the stirring device 14 to form a suspension of the polymer in the poor solvent, and the suspension is output from the slurry outlet 13 for filtration, separation and drying, so that the solid powder of the dihydroxyl polyphenyl ether can be obtained in high yield. The separating out device further comprises a filtering device and a drying device, and the slurry pump 4 is sequentially connected with the filtering device and the drying device and is used for filtering and separating out the output slurry and drying the solid separated by filtering.

As shown in fig. 2, the stirring device 14 preferably comprises a motor 15, a drive spindle 16 and a double-layered helical blade 17 arranged on the drive spindle 16.

Preferably, the inner helical blade of the double-layer helical blade 17 is directed outward in the helical conveying direction, and the outer helical blade is directed inward in the helical conveying direction. Both inward and outward of the drive spindle 16.

The inner and outer helical blades of the stirring device on the transmission main shaft 16 drive the materials in the barrel body, so that the stirring device turns the materials in the barrel body in a large range. When the concentrating mixer 1 works, the inner helical blades drive the materials close to the axis to rotate, the materials are axially pushed from inside to outside to convey the materials outwards, the outer helical blades drive the materials close to the barrel wall to rotate, and the materials are axially pushed from both sides to inside to gather inwards, so that the materials can be powdered in a short time to form uniform suspension. The materials form a low-power and high-efficiency mixing environment under the convection motion of the double-layer helical blades 17.

More preferably, the stirring device 14 further comprises a frame stirring structure 18 arranged on the transmission main shaft 16, wherein the distance between the outer edge of the frame stirring structure 18 and the inner wall of the concentrating mixer 1 is 0-50 mm, preferably 0-20 mm. The frame stirring structure 18 can function as a scraper to clean the materials adhered to the inner wall of the concentrating mixer 1 and continuously mix under the action of the double-layer helical blades 17.

As shown in fig. 1 and 2, the main body of the concentrating mixer 1 is preferably a cylinder, and the lower part is a cone.

As shown in fig. 1 and 2, preferably, the heating means comprises a jacket 19 provided outside the concentrating mixer 1, the jacket 19 comprising a hot fluid inlet 19-1 at the top and a cold fluid outlet 19-2 at the bottom. Specifically, the hot fluid input into the hot fluid inlet 19-1 may be hot water or heat conducting oil, the hot fluid heats the materials in the concentrating mixer 1, so that toluene in the materials is evaporated and output from the toluene outlet 12, and the heat-exchanged fluid is output from the cold fluid outlet 19-2 to the jacket 19, and the corresponding fluid may be cold water or cold heat conducting oil.

According to the precipitation apparatus of the present utility model, preferably, a vacuum pump 5 is connected to the top of the toluene collection tank 3 to form a negative pressure condition for reducing the temperature at which toluene evaporates.

According to the precipitation device of the utility model, preferably, the toluene collecting tank is connected with a toluene conveying pump 6 at the bottom, and toluene can be conveyed to the reaction preparation device for recycling.

According to the precipitation apparatus of the present utility model, preferably, the precipitation apparatus further comprises a poor solvent storage tank 7 and a poor solvent metering pump 8, and the poor solvent storage tank 7 is connected to the poor solvent metering pump 8 and the poor solvent inlet 11 in sequence, for quantitatively adding a poor solvent, such as methanol, to the concentrating mixer 1.

In another aspect, the utility model provides a system for producing polyphenylene ether, comprising a reaction preparation device and the precipitation device; and each raw material in the reaction preparation device reacts to generate the polyphenyl ether.

The process flow for carrying out polyphenyl ether by using the production system specifically comprises the following steps:

The specific process of the third step comprises the following steps: after the second step of reaction is completed, the obtained polymer solution is added into a concentrating mixer 1, the polymer solution is heated by a heating device, toluene serving as a good solvent is evaporated under a certain negative pressure condition to obtain viscous polymer fluid, and the evaporation amount of the good solvent is controlled to control the viscous liquid to have certain fluidity. When the temperature is reduced to 30-50 ℃, adding a poor solvent with the polymer amount being 2-6 times, stirring for 0.5-4 h to obtain a highly dispersed polymer particle suspension, outputting the suspension from a slurry outlet 13, filtering, and drying to obtain the double-end hydroxyl polyphenyl ether powder.

The production of polyphenylene ether was carried out using the above production system, and the following specific application examples are provided herein.

Application example 1:

to a 1 liter jacketed reactor equipped with an oxygen-containing gas distribution tube, turbine blade stirrer and baffles at the bottom, and an exhaust gas condenser at the top, 0.25g of copper chloride dihydrate, 3.6179g of di-N-butylamine, 9.5937g of N, N' -tetramethylpropanediamine, 480g of toluene and 120g of 2, 6-xylenol were added. Introducing oxygen from a gas distribution pipe under sufficient stirring at a flow rate of 60mL/min; at the same time, the polymerization temperature was adjusted to 40℃by introducing a heating medium into the reactor jacket and maintaining such temperature; no material was found to adhere to the reactor walls during the polymerization. The oxygen flow was stopped after 120 minutes, calculated from the start of oxygen introduction. 0.3% of p-toluenesulfonic acid catalyst was added relative to 1mol of diphenol, heated to 50℃and 20g of bisphenol A was slowly added while maintaining the temperature at 50℃to react for 3 hours to obtain a polymer solution.

The polymer solution was transferred to a mixer-disperser 1 while it was hot, the temperature was increased to 40℃and the pressure was 80mbar, the solvent toluene was distilled off until after 420g toluene was collected, the polymer solution temperature was reduced to 40℃and 360g methanol was added and stirred at high speed (400 rpm) for two hours to give a white suspension, the wet polyphenylene ether was obtained by filtration and dried in a vacuum oven at 110℃to give a dry polyphenylene ether sample.

Application example 2:

the procedure of application example 1 was repeated, changing the flow rate of oxygen to 180mL/min. No sticking phenomenon on the reactor wall was found to occur during the polymerization reaction. The reduced viscosity of the obtained polymer and the yield of the polymer were reduced, and the polymer precipitation effect of the mixer-disperser was equivalent to that of application example 1.

Application example 3:

the procedure of application example 1 was repeated, and the amount of toluene as a solvent distilled off from the polymer solution in the mixer-disperser 1 was changed, and after collecting 320g of toluene, the yield of the obtained polymer was reduced to 75%.

Application example 4:

application 2 was repeated, but the phenol was instead a mixture of 126g of 2, 6-xylenol and 54g of 2,3, 6-tricresyl. No sticking phenomenon on the reactor wall was found to occur during the polymerization. The reduced viscosity of the obtained polymer and the yield of the polymer were reduced, and the polymer precipitation effect of the mixer-disperser was equivalent to that of application example 1.

Application example 5:

application 2 was repeated but using a mixture of 126g of 2, 6-xylenol and 54g of 2, 6-diphenylphenol as phenolic monomer; in the composition of the catalyst, 0.1690g of N, N' -tetramethyl ethylenediamine was used as a diamine component; and the polymerization temperature was changed to 60℃and the polymerization time was changed to 180 minutes. The reduced viscosity of the obtained polymer was equivalent to that of application example 2, the yield of the polymer was also equivalent, and the polymer precipitation effect of the mixer-disperser was equivalent to that of application example 1.

Comparative application example 1:

the experiment of application example 1 was repeated, but the concentration and precipitation of the polymer solution were carried out using a rotary evaporator (without a built-in stirring paddle), under which conditions the polymer was first adhered to the inner wall of the evaporation bottle and formed large agglomerates after a period of time, so that the subsequent operation was not carried out.

The polymer samples obtained in the above application examples have molecular weights, molecular weight distributions, yields, etc., and the summarized test data are shown in Table 1.

The nuclear magnetic resonance spectrum of the product is shown in figure 3, wherein the 1.6ppm area is the displacement of hydrogen on a coupling agent methyl group, the 2.0ppm area is the chemical displacement of hydrogen on a polymer main chain benzene ring, the 4.2ppm area is the chemical displacement of hydrogen on two side hydroxyl groups, and the 6.5-7.1ppm area is the chemical displacement of hydrogen on the polymer main chain benzene ring.

Table 1 comprehensive table of experimental results

It should be understood that the foregoing examples of the present utility model are provided merely for clearly illustrating the present utility model and are not intended to limit the embodiments of the present utility model, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present utility model as defined by the appended claims.

Claims

1. The precipitation device of the polyphenyl ether is characterized by comprising a concentrating mixer, a toluene condenser, a toluene collecting tank and a slurry pump;

2. The polyphenylene ether precipitation device according to claim 1, wherein the stirring device comprises a motor, a transmission spindle and a double-layer helical blade disposed on the transmission spindle;

the spiral conveying direction of the inner spiral blade of the double-layer spiral blade is outward, and the spiral conveying direction of the outer spiral blade is inward.

3. The polyphenylene ether precipitation device according to claim 2, wherein the stirring device further comprises a frame stirring structure disposed on the transmission main shaft, and a distance between an outer edge of the frame stirring structure and an inner wall of the concentration mixer is 0 to 50mm.

4. The polyphenylene ether precipitation device according to claim 1, wherein the main body of the concentrating mixer is a cylinder, and the lower part is a cone.

5. The polyphenylene ether precipitation device according to claim 1, wherein the heating device comprises a jacket disposed outside the concentrating mixer, the jacket having a top portion comprising a hot fluid inlet and a bottom portion comprising a cold fluid outlet.

6. The polyphenylene ether precipitation device according to claim 1, wherein a vacuum pump is connected to the top of the toluene collection tank.

7. The polyphenylene ether precipitation device according to claim 6, wherein a toluene transfer pump is connected to the bottom of the toluene collection tank.

8. The apparatus for precipitating polyphenylene ether according to claim 1, further comprising a poor solvent tank and a poor solvent metering pump, wherein the poor solvent tank is connected to the poor solvent metering pump and the poor solvent inlet in this order.

9. The polyphenylene ether precipitation device according to claim 1, further comprising a filtration device and a drying device, wherein the slurry pump is connected to the filtration device and the drying device in this order.

10. A system for producing polyphenylene ether, characterized in that the production system comprises a reaction producing apparatus and a precipitation apparatus of polyphenylene ether according to any one of claims 1 to 9.