JPH07330910A - Method for continuous bulk polymerization of polycondensation polymer and apparatus therefor - Google Patents

Abstract

PURPOSE:To provide a method whereby a reaction liq. is inhibited from sticking to the surface of a rotating shaft and thus from together with the shaft and a high-quality method whereby a reaction liq. is inhibited from polycondensation polymer can be produced by using a stirring device of a specific shape. CONSTITUTION:A polycondensation polymer is produced by continuous bulk polymn. by using stirring vessels connected to each other. The intermediate is produced by using a stirring device which has the inlet of a reaction liq., the outlet of the intermediate, and the outlet of volatiles installed at the side, at the lower part, and at the upper part of a vertical cylindrical or conical container, respectively, has a rotating edge shaft at the upper part of the inside of the container and has a stirrer blade which has rectangular frames, is connected to the shaft, and stirs the liq. while scraping the inner wall of the container. The intermediate is subjected to the final polymn. by using an apparatus which has a horizontal container equipped with the inlet of the intermediate, the outlet of the final product, and the outlet of volatiles installed at the lower part of the one end of the container in the longitudinal direction, at the lower part of the other end, and at the upper part, respectively, has two rotating edge shafts extending over both ends in the longitudinal direction inside the container, and has two stirring members which are formed by connecting rodlike rectangular frames to the two shafts and arranged nearby into each other so that they rotate while engaging into each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stirring highly viscous substances, and more particularly to a method suitable for bulk polymerization of polycondensation polymers such as polyethylene terephthalate and polycarbonate.

[0002]

2. Description of the Related Art Conventionally, a continuous bulk polymerization method for producing a polycondensation polymer by connecting a plurality of stirring tanks has been disclosed in Japanese Patent Laid-Open No.
As disclosed in Japanese Patent No. 153925, a pre-stage polymerization is carried out in a tank type stirring tank equipped with a stirring blade mounted on a vertical rotating shaft, and a discontinuous stirring blade mounted on a horizontal rotating shaft at a substantially right angle. Some of the horizontal stirring polymerization tanks have a second-stage polymerization.

[0003]

However, the above-mentioned prior art does not sufficiently consider the viscosity of the liquid to be treated, which increases with the progress of the polymerization.
There is a problem in that the liquid to be treated that has become s or more adheres to the surface of the vertical rotating shaft of the tank-type stirring tank or the horizontal rotating shaft of the horizontal stirring polymerization tank to cause co-rotation, which causes quality deterioration.

An object of the present invention is to provide a method for preventing a liquid to be treated from adhering to the surface of a rotating shaft to co-rotate therewith, thereby producing a polycondensation polymer of good quality.

[0005]

The above object is to provide a structure in which a vertical rotating shaft is provided inside a vertical cylindrical container, and a plurality of rectangular frame stirring blade constituent elements are connected to the rotating rotary shaft. To form a stirring blade, and the stirring blade configured to scrape and stir the inner wall of the container to produce an intermediate polymer, and the intermediate polymer is produced in a longitudinal direction inside the substantially horizontal container. Two rotating ear shafts are arranged side by side, a plurality of rod-shaped rectangular frames are connected between the rotating ear shafts to form a stirring member, and the stirring members of the mating members are engaged with each other so that the stirring members engage with each other. Achieved by final polymerization with a device that rotates in close proximity to the inside.

[0006]

[Operation] Inside the vertical cylindrical container, the liquid to be treated is scraped and agitated by the rectangular frame that does not have a rotating shaft at the center to thoroughly scrape the inner wall of the container, and then the rod-shaped container without a rotating shaft inside the horizontal container. By rotating the rectangular frames close to the inside of the other stirring member so that they mesh with each other, it is possible to prevent the high-viscosity liquid from adhering to the rotating shaft and to stir without dead space.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention is shown in FIGS. FIG. 1 shows the overall flow, 10 is a vertical cylindrical stirring device, and 30 is a horizontal stirring device. Details of the vertical cylindrical stirring device 10 are shown in FIGS. 2 and 3. In the figure, the stirring tank main body 11 is a cylindrical container having a circular cross section, and although not shown, the outside has a heating medium jacket capable of heating and cooling. A rotary power transmission shaft (hereinafter, referred to as a rotary ear shaft) 12 is provided from the upper portion inside the main body 11, and a stirring blade 13 that connects rectangular frames 13a, b and c is attached to the lower portion of the rotary ear shaft 12. ing. Rectangular frame 13
a, b, and c are connected to each other with a phase angle of 90 degrees to form the stirring blade 13, and the vertical member 1 of each rectangular frame is connected.
4 is inclined in the direction of scraping up the object to be treated on the inner wall of the container.

The rectangular frame 13 rotates along the inner wall of the stirring tank body 11. At this time, since the vertical member 14 is configured so as to scrape up the processing liquid with respect to the rotational direction, the liquid is scraped up along the tank wall.

An intermediate polymer withdrawal screw 15 is attached to the lower portion of the main body 11 and is connected to a lower drive unit 16. Further, an inlet nozzle 17 for the prepolymer, an outlet nozzle 18 for the intermediate polymer, and an outlet nozzle 19 for the volatile matter are attached to the side surface, the lower portion, and the upper portion of the main body 11, respectively.
The volatile matter outlet nozzle 19 is connected to a condenser and a vacuum pump (not shown) by piping.

Next, details of the horizontal stirring device 30 are shown in FIGS. 4, 5 and 6. In the figure, 31 is a horizontally long cylindrical main body container, the outer periphery of which is covered with a heat medium jacket (not shown). Two rotating ear shafts 32 are arranged side by side at both ends in the longitudinal direction inside the container 31, and a plurality of rod-shaped rectangular frames 33 are connected between the respective rotating ear shafts 32 to form a stirring member 34. Agitating member 3 on the other side so that 34 meshes with each other
Rotate close to the inside of 4. In this embodiment, a plurality of rod-shaped rectangular frames 33 inside the container 31 are connected to each other at a phase angle of 90 degrees to form a stirring member 34.
4 rotate so that they mesh with each other at a phase angle of 45 degrees.
The end of the rotating ear shaft 32 is connected to a driving device (not shown),
The stirring member 34 rotates in a direction to lift the liquid inside.

An intermediate polymer inlet nozzle 35 is provided below one end (left side in FIG. 4) of the main body container 31, and a gear pump 36 and a final polymer outlet nozzle 37 are provided below the other end.
A volatile matter outlet nozzle 38 is provided at the top of the container 31. The volatile matter outlet nozzle 38 is connected by piping to a condenser and a vacuum pump (not shown).

In such an apparatus, the prepolymer 1 is continuously supplied from the inlet nozzle 17 of the vertical cylindrical stirrer 10. The inside of the main body 11 is depressurized, and is agitated by the agitating member 14 to promote the surface renewal of the prepolymer 1 and the polycondensation reaction proceeds, and the volatile matter is removed from the volatile matter outlet nozzle 19 to remove the prepolymer 1 It becomes a highly viscous liquid. Then, the intermediate polymer 2 having a high viscosity is extracted by the extraction screw 15 through the outlet nozzle 18, and is continuously supplied to the horizontal stirring device 30 from the inlet nozzle 35. The pressure inside the main body 31 of the horizontal stirring device 30 is also reduced, and the stirring member 3
The surface of the intermediate polymer 2 is agitated by being stirred at 4, and the polycondensation reaction proceeds further. During this time, the volatile matter by-produced by the reaction is removed from the volatile matter outlet nozzle 38 to remove the intermediate polymer 2.
Becomes a final polymer 3 having a higher viscosity. Then, the final polymer 3 is discharged to the outside of the system by the gear pump 36 through the outlet nozzle 37.

In the meantime, the prepolymer 1 in the vertical cylindrical container 11 is scraped and agitated by the rectangular frame 13 having no central axis of rotation so that the inner wall of the container 11 is thoroughly agitated. Due to the inclination of the direction member 14, the prepolymer 1 is scraped along the inner wall of the container 11 and falls at the center of the container without the rotation axis. As a result, it is possible to prevent the co-rotation of the intermediate polymer 2, which has become highly viscous due to the progress of the reaction, on the rotating shaft, and is stirred without dead space.

Subsequently, in the horizontal container 30, the rod-shaped rectangular frames 33 having no rotation axis rotate in close proximity to the inside of the stirring member 34 on the mating side so as to mesh with each other. As a result, the final polymerization product 3 in which the reaction proceeded further and the viscosity became ultra high
Can be prevented from adhering to the rotating shaft and agitated without dead space.

When polyethylene terephthalate is polymerized with such an apparatus, for example, the average molecular weight is 5,000 to 5,000.
10000 of the initial polymerization product 1 is continuously supplied from the inlet nozzle 17 of the vertical cylindrical container 11 and stirred by the rectangular frame 13 to evaporate and remove volatile substances such as ethylene glycol generated in the polymerization reaction, and the polycondensation reaction Advanced average molecular weight of 10,000
The intermediate polymer 2 has a high viscosity of ˜15,000. Volatile substances such as ethylene glycol separated during this time are discharged from the outlet nozzle 1
It is discharged from 9. The operating conditions at this time are, for example, a temperature of 26
0 to 300 ° C, pressure 0.01 to 10 kPa, rotation speed 3 to
It is performed in the range of 30 rpm. Then, the intermediate polymer 2 is extracted by the extraction screw 15 through the outlet nozzle 18, and continuously supplied from the inlet nozzle 35 to the horizontal stirring device 30. Then, in the horizontal stirrer 30, the surface of the intermediate polymer 2 is stirred by being stirred by the stirring member 34, and the polycondensation reaction proceeds further. During this period, volatile substances such as ethylene glycol, which are a by-product of the reaction, are removed from the volatile substance outlet nozzle 38, and the intermediate polymer 2 has an average molecular weight of 200.
The final polymer 3 having a higher viscosity of 00 to 35,000 is obtained and discharged out of the system. The operating conditions at this time are, for example, a temperature of 26
0 to 300 ° C, pressure 0.01 to 10 kPa, rotation speed 3 to
It is performed in the range of 30 rpm. In the above operation, since the high-viscosity polymers 1 to 3 are stirred in the respective containers 10 and 30 in a substantially complete self-cleaning state, deterioration due to retention does not occur, and high quality polymer products can be obtained.

In the case of polymerizing polycarbonate with this apparatus, the same method as for the above polyethylene terephthalate is used.
The initial polymer 1 having an average molecular weight of 5,000 to 10,000 is continuously supplied from the inlet nozzle 17 of the vertical cylindrical container 11 and stirred in the rectangular frame 13 to evaporate and remove volatile substances such as phenol generated in the polymerization reaction. , The average molecular weight is 10,000 to
20000 of the intermediate polymer 2 was obtained, and subsequently, in a horizontal stirrer 30, the mixture was stirred by a stirring member 34 to evaporate and remove volatile substances such as phenol, and the average molecular weight was 30,000 to 40,000.
The highly viscous final polymer 3 can be continuously produced. In this case, the reaction temperature is recommended to be in the range of 270 to 320 ° C. FIG. 7 shows an example of changes in melt viscosity of the polymer (the initial polymer 1, the intermediate polymer 2, and the final polymer 3) when the polycarbonate is continuously polymerized in this manner.

In addition to the above, the present invention can be applied to continuous bulk polymerization of polycondensation resins such as polybutylene terephthalate and polyamide.

[0018]

According to the present invention, the high-viscosity liquid to be treated is prevented from adhering to the surface of the rotating shaft and co-rotating, and can be agitated in an almost completely self-cleaning state, so that there is no deterioration due to retention and the quality is high. It is possible to continuously produce a high-molecular weight polycondensation polymer.

[Brief description of drawings]

FIG. 1 is an overall flow chart showing an embodiment of the present invention.

FIG. 2 is a front sectional view of the vertical cylindrical stirring device of FIG.

3 is a sectional view taken along line III-III in FIG.

FIG. 4 is a plan sectional view of the horizontal stirring device of FIG.

5 is a sectional view taken along line VV of FIG.

6 is a sectional view taken along line VI-VI of FIG.

FIG. 7 is a diagram showing an example of changes in melt viscosity when polycarbonate is continuously polymerized.

[Explanation of symbols]

1 ... initial polymer, 2 ... intermediate polymer, 3 ... final polymer, 1
0 ... Vertical cylindrical stirring device, 11 ... Stirring tank body, 12 ...
Rotating ear shaft, 13 ... Rectangular frame, 14 ... Longitudinal member, 15
... withdrawal screw, 17 ... initial polymer inlet nozzle, 18 ... intermediate polymer outlet nozzle, 19 ... volatile material outlet nozzle, 30 ... horizontal stirring device, 31 ... horizontally long cylindrical main body container, 32 ... rotating ear Axis, 33 ... Rod-shaped rectangular frame, 34 ...
Stirring member, 35 ... Intermediate polymer inlet nozzle, 36 ... Gear pump, 37 ... Final polymer outlet nozzle, 38 ... Volatile outlet nozzle

Claims (12)

[Claims] 1. A continuous bulk polymerization method for producing a polycondensation polymer by connecting a plurality of stirring tanks, wherein a liquid to be treated is provided on a side surface, a lower portion and an upper portion of a substantially vertical cylindrical or cone-shaped container. It has an inlet, an outlet, and an outlet for volatile matter, and has a rotating ear shaft in the upper part inside the container, and scrapes the inner wall of the container with a stirring blade connected to the rotating ear shaft and connecting a plurality of rectangular frames. An intermediate polymer is produced by a stirrer configured to stir, and the intermediate polymer is introduced into the substantially horizontal container longitudinal direction at one end lower part, the other end lower part and upper part, respectively, of the liquid to be treated, the outlet and the volatile matter. And a plurality of rod-shaped rectangular frames are connected between the rotating ear shafts to form a stirring member, and the stirring member is formed. Rotate close to the inside of the other stirring member so that they mesh with each other. The final polymerized by the continuous bulk polymerization method polycondensation polymers, characterized in that the optimum stirring effect in response to increase in the viscosity of the liquid to be treated is obtained by a device for. 2. A continuous bulk polymerization method for producing a polycondensation polymer by connecting a plurality of stirring tanks, wherein a side surface, a lower portion and an upper portion of a substantially vertical cylindrical or cone-shaped container are filled with a liquid to be treated, respectively. It has an inlet, an outlet, and an outlet for volatile matter, and has a rotating ear shaft in the upper part inside the container, and a plurality of frame-shaped members having no rotating shaft are connected to the center of the container by connecting to the rotating ear shaft. An intermediate polymer is produced by a stirrer configured to scrape and stir the inner wall of the container with a stirring blade, and the intermediate polymer is applied to the substantially horizontal container at one end lower part, the other end lower part and the upper part in the longitudinal direction of the container, respectively. It has an inlet and an outlet for the treatment liquid and an outlet for volatile matter, and has two rotating ear shafts arranged side by side at both ends in the longitudinal direction inside the container. The frame-shaped members are connected to form a stirring member, and the stirring members are The final polymerization is performed by a device that rotates close to the inside of the other stirring member so that the optimum stirring effect can be obtained in response to the increase in the viscosity of the liquid to be treated. A continuous bulk polymerization method for a condensation polymer. 3. The stirring blade according to claim 1, wherein a plurality of rectangular frames are connected inside a substantially vertical cylindrical or cone-shaped container with a phase angle of 90 degrees. To form a vertical member of the rectangular frame to incline, to produce an intermediate polymer with a stirring device configured to rotate in a direction of scraping the object to be treated on the inner wall of the container by the stirring blade,
A continuous bulk polymerization method of a polycondensation polymer, which is subsequently subjected to final polymerization by the horizontal apparatus according to claim 1. 4. The polymerization method according to claim 1 or 2, wherein an intermediate polymerization product is produced by the vertical stirring apparatus according to claim 1, and subsequently, a plurality of rod-shaped rectangular frames inside a horizontal container are 90 degrees apart from each other. Polycondensation resin to be finally polymerized by a device that rotates in close proximity to the inside of the other stirring member so that the stirring members mesh with each other at a phase angle of 45 degrees. Continuous bulk polymerization method of. 5. A continuous bulk polymerization method of polyethylene terephthalate, characterized in that the temperature of the polymerized product is in the range of 260 to 300 ° C. in the polymerization method according to any one of claims 1 to 4. 6. A continuous bulk polymerization method for a polycarbonate according to any one of claims 1 to 4, wherein the temperature of the polymer is in the range of 270 to 320 ° C. 7. An initial polymer having an average molecular weight of 5,000 to 10,000 is polycondensed to have an average molecular weight of 10,000 to 15
A step of producing an intermediate polymer having an average molecular weight of 20,000
Producing a high viscosity polymer of 35000,
A polymerization method comprising: 8. The polymerization method according to claim 7, wherein the polymer is polyethylene terephthalate. 9. An initial polymer having an average molecular weight of 5,000 to 10,000 is polycondensed to have an average molecular weight of 10,000 to 15.
And a means for producing an intermediate polymer having an average molecular weight of 20,000
And a means for producing a high-viscosity polymer of 35,000. 10. An initial polymer having an average molecular weight of 5,000 to 10,000 is polycondensed to have an average molecular weight of 10,000 to 2
0000 to produce an intermediate polymer, and the intermediate polymer is polycondensed to have an average molecular weight of 30,000-
Producing a high viscosity polymer that is 40,000;
A polymerization method comprising: 11. The polymerization method according to claim 10, wherein the polymer is polycarbonate. 12. An initial polymer having an average molecular weight of 5,000 to 10,000 is polycondensed to have an average molecular weight of 10,000 to 2
And an average molecular weight of 30,000 to polycondensate the intermediate polymer with the above-mentioned intermediate polymer.
And a means for producing a high-viscosity polymer of 40,000.