JPH093200A - Apparatus for continuous production of polycondensation polymer and method therefor - Google Patents

Abstract

(57) [Summary] [Object] The present invention is intended to simplify a manufacturing apparatus and a manufacturing method of a polycondensation resin. [Structure] A transesterification tank and an initial polymerization tank are vertically connected to each other to form a two-column system including a first manufacturing apparatus having an integrated structure and a second manufacturing apparatus which is a vertical final polymerization tank. [Effect] The apparatus price can be reduced and the installation space of the apparatus can be reduced by reducing the number of components of the apparatus and the number of assembling steps.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and method for producing polymer resins, and more particularly to an apparatus and method suitable for polymerizing polycondensation polymers such as polyethylene terephthalate and polycarbonate.

[0002]

2. Description of the Related Art Conventional polyethylene terephthalate (PE
As the polymerization method of T), a manufacturing process including a transesterification tank, an initial polymerization tank, and a polymerization tank is used as described in Process Compilation (1970) P892 edited by Japan Chemical Engineering Association. In an actual process, it is general that the transesterification tank is divided into several units, and the initial polymerization tank is also divided into two and used.

[0003]

An object of the present invention is to integrate a part of the transesterification tank and the initial polymerization tank into a first production apparatus, and integrate the rest of the initial polymerization tank and the final polymerization step into a second one.
As a manufacturing device, by reducing the number of reaction tanks, the number of drive parts, piping points, seal parts, etc. of each stirring tank is reduced.

[0004]

[Means for Solving the Problems] The above problems and objectives are to install a transesterification tank in an upper tower and an initial polymerization tank in a lower tower to integrate them into a first manufacturing apparatus, an intermediate polymerization tank and a final polymerization tank. By constructing a continuous polycondensation polymer manufacturing device with a vertical type second manufacturing device that integrates the above, the number of components and materials of the manufacturing device can be reduced, the number of assembly pipes for the device can be reduced, and the heat insulation and installation cost can be reduced. It is achieved by reducing

[0005]

The raw material continuously supplied from the inlet nozzle of the first manufacturing apparatus undergoes transesterification in the upper tower to form an oligomer, which is then supplied to the lower tower to evaporate volatile matter in each stirring chamber in the lower tower. However, it flows to the lower side of the lower tower, the polycondensation reaction proceeds efficiently, and the degree of polymerization is increased. Further, it is supplied to the second manufacturing apparatus, and is subjected to stirring and surface renewal action by the stirring member in the doughnut-shaped stirring chamber, and is sequentially moved to the lower stirring chamber, and the efficient blade reaction proceeds to increase the degree of polymerization to the target.

[0006]

FIG. 1 shows an embodiment of the present invention. In the figure, the left side shows the first manufacturing apparatus, the right side shows the second manufacturing apparatus, 1 is a vertically long cylindrical first manufacturing apparatus body, the outer periphery of which is covered with a heat medium jacket (not shown), The container body is divided into two inside, the transesterification tank 2 is formed on the upper tower side, and the initial polymerization tank 3 is formed on the lower tower side. The raw material 13 enters through a supply nozzle 4 provided in the lower portion of the transesterification tank 2 and is agitated and mixed by a low-viscosity agitating blade 6 to accelerate the esterification reaction. A nozzle 11 for removing a by-product 12 produced by a transesterification reaction is attached to the upper part of the transesterification tank 2, and is separated and recovered by a condenser on the downstream side. The transesterification tank 2 and the initial polymerization tank 3 are connected by a connecting pipe 7, and the upper end side thereof is the transesterification tank 2
It is raised to the upper liquid surface, and the lower end side is the initial polymerization tank 3
Is installed in the liquid pool of the tray 8a provided in the upper part of the tank, and a flow rate adjusting valve 9 for adjusting the liquid level height of the tray 8a is provided in the middle of the connecting pipe 7 and Is controlled so that the liquid surface of the liquid has a predetermined height. The vapor phase portion of the initial polymerization tank 3 is provided with a volatile matter extraction nozzle 10 for removing the volatile matter 14 generated by the polymerization reaction from the liquid surface of each tray and evaporated.
A vacuum pump (not shown), a condenser (not shown) for collecting by-products, and the like are provided on the downstream side of the volatile matter removal nozzle 10 in order to reduce the pressure in the tank to a reduced pressure atmosphere. As shown in the figure, in this embodiment, the initial polymerization tank 3 has no stirring blade member inside. Instead of this agitating blade, downflow trays are installed in multiple stages to obtain a large surface renewal action. Inside the initial polymerization tank 3, ring-shaped trays 8a and cylindrical trays 8b are alternately arranged. On the inner peripheral upper surface side of the ring-shaped tray 8a and the outer peripheral upper surface side of the cylindrical tray 8b. Is provided with one or a plurality of notches, the processing liquid flows to the tray on the downstream side, reaches the bottom of the initial polymerization tank 3, and the initial polymerization product 15 is taken out from the extraction nozzle 5, No. 2 manufacturing equipment. In the figure, 30
Is a vertically elongated second manufacturing apparatus main body, the outer periphery of which is covered with a heat medium jacket (not shown), and the rotary shaft 32 is attached in the inner longitudinal direction. The rotary shaft 32 is provided with a drive device 31 on its upper part, and is supported by a lower bearing 42 on the lower part of the main body 30. A ring-shaped member 38 having a plurality of L-shaped cross sections is attached inside the main body 30, and a donut-shaped stirring chamber 39 is formed between the ring-shaped members 38. A rectangular frame-shaped stirring member 37 for scraping the inner wall of each stirring chamber 39
Is attached to the rotary shaft 32, and each stirring member 37
Rotates by scraping the inner wall surface of the stirring chamber 39. In the lower part of the side surface of the uppermost stirring chamber 39, an inlet nozzle 33 for the liquid to be treated is provided.
Is attached, and an outlet nozzle 34 for the liquid to be treated is attached to the bottom surface of the main body 30 of the lowermost stirring chamber 39b. Further, a volatile matter outlet nozzle 35 is provided above the lowermost stirring chamber 39b of the main body 30, and is connected to a condenser and a vacuum pump (not shown) by piping. Reference numeral 43 is a shaft sealing device for the rotating shaft 32.

The case of producing polyethylene terephthalate with the above constitution will be described. As a raw material of polyethylene terephthalate, a mixture of terephthalic acid and ethylene glycol or a mixture of dimethyl terephthalate and ethylene glycol is generally used. These raw materials are supplied to the transesterification tank 2 from the inlet nozzle 4 of the first manufacturing apparatus 1. The transesterification tank has a stirring blade rotation speed of 10
The transesterification reaction is performed at 0 to 200 rpm, a temperature of 200 ° C. to 270 ° C., and a pressure of atmospheric pressure or under pressure. By-products (water and ethylene glycol or methanol and ethylene glycol) produced by the transesterification reaction are collected by a by-product collection condenser (not shown) installed upstream of the by-product removal nozzle 11. On the other hand, bisbetahydroxyethyl terephthalate produced by transesterification is supplied from the upper end of the connecting pipe 7 provided on the surface of the treatment liquid to the upper tray on the lower tower side. At this time, since the operating pressure of the lower tower is 1.3 kPa to 133 Pa, the flow rate is adjusted by the flow rate adjusting valve 9 provided in the middle of the connecting pipe 7 so that the liquid height of the tray 8a is always constant. The processing liquid is the uppermost ring-shaped tray 8a.
From the cylindrical tray 8b to the ring-shaped tray 8a. At this time, since the treatment liquid is in a reduced pressure atmosphere, a by-product generated by the polymerization reaction is vaporized and vigorous foaming occurs. As a result, the treatment liquid is mixed and at the same time strongly receives a surface renewal action to accelerate the polymerization reaction. Will be done. By providing such a tray structure in a plurality of stages, the residence time necessary for the reaction can be secured and the desired degree of polymerization can be obtained. Further, the initial polymerization product 15 is continuously supplied from the inlet nozzle 33 of the second manufacturing apparatus 30, and the surface is renewed by stirring with the stirring member 37 to evaporate and remove volatile substances such as ethylene glycol generated in the polymerization reaction, thereby performing polycondensation. The reaction proceeds and becomes the high-viscosity final polymer 41. Volatile substances such as ethylene glycol separated during this time are discharged from the outlet nozzle 40. The operating conditions at this time are, for example, temperature 2
60 to 300 ° C, pressure 0.01 to 10 kPa, rotation speed 3
It is performed in the range of ˜30 rpm. Then, the polymer is discharged from the system through the outlet nozzle 34. At this time, the final polymer 4
No. 1 is stirred in each stirring chamber 39 in a substantially complete self-cleaning state, and a downcomer 36 that connects the side surfaces of adjacent stirring chambers 39 is provided, and the liquid to be treated in the upper stirring chamber 39 overflows. It is configured to flow into the bottom of the lower stirring chamber 39, and uniform stirring is easily obtained,
Further, in each agitating chamber, the treatment liquid undergoes a good surface renewal due to the thinning, so that it is possible to efficiently obtain a high quality product polymer without deterioration due to retention.

Similarly, the present invention can be applied to continuous bulk polymerization of polycondensation resins such as polyamide and polycarbonate.

According to another preferred embodiment of the present invention, as shown in FIG. 2, the transesterification tank 2 and the second transesterification tank 2 of the first manufacturing apparatus are used.
Since the structure and operation of the manufacturing apparatus are the same, description thereof will be omitted. The initial polymerization tank 3 of the present invention is the transesterification tank 2 of the upper tower.
Is connected by a connecting pipe 7 and a flow rate adjusting valve 9 is provided between them to control the liquid level on the liquid tray 24 provided in the upper part of the lower tower to a predetermined height. The liquid tray has a ring shape with a space in the center and is configured to have the same atmosphere as the downstream side. On the downstream side thereof, stirring chambers 20 forming a ring-shaped liquid pool are installed in multiple stages, and a stirring member 22 for thoroughly stirring the inside of the stirring chamber 20 is provided for each stirring chamber, and the center of the initial polymerization chamber is provided. It is connected to a stirring shaft 23 installed in the section. Further, each stirring chamber 20 is provided with a connecting pipe 21 that connects the upper side liquid surface of each upper tray and the bottom side surface portion of the stirring chamber, so that the processing liquid always flows out from the liquid surface of the stirring chamber, The flow is supplied from the bottom side of the.

The case of producing polyethylene terephthalate with the above constitution will be described. As a raw material of polyethylene terephthalate, a mixture of terephthalic acid and ethylene glycol or a mixture of dimethyl terephthalate and ethylene glycol is generally used. These raw materials are supplied from the inlet nozzle 4 to the transesterification tank 2.
The transesterification tank has a stirring blade rotation speed of 100 to 200 rp
m, temperature 240 ° C. to 260 ° C., pressure is atmospheric pressure or under elevated pressure to carry out the transesterification reaction. By-products (water and ethylene glycol or methanol and ethylene glycol) produced by the transesterification reaction are collected by a by-product collection condenser (not shown) installed upstream of the by-product removal nozzle 11. On the other hand, bisbetahydroxyethyl terephthalate produced by transesterification is supplied from the upper end of the connecting pipe 7 provided on the surface of the treatment liquid to the upper tray on the lower tower side. At this time, since the operating pressure of the lower tower is 13000 Pa to 133 Pa, the tray 24 is set by the flow rate adjusting valve 9 provided in the middle of the connecting pipe 7.
The flow rate is adjusted so that the liquid height is always constant.
The treatment liquid on the uppermost tray flows to the stirring chamber 20 immediately downstream through the connecting pipe 21. The treatment liquid supplied to the stirring chamber 20 is stirred by the stirring member 22 to accelerate the polymerization reaction. In addition, the stirring action by the stirring blade activates the surface renewal action, and the reaction proceeds further. The reaction by-product generated at this time is removed from the volatile matter extraction nozzle 10 for removing the volatile matter 14. The treatment liquid after a predetermined residence time has elapsed in the initial polymerization tank is collected in the lower portion of the tank, the initial polymerization product 15 is taken out from the withdrawing nozzle 5, and further proceeds to the next vertical final polymerization tank (second manufacturing apparatus) for polymerization. The degree is increased.

[0011]

According to the present invention, the polycondensation resin is formed by connecting the first manufacturing apparatus having the transesterification tank and the initial polymerization tank integrally formed with the second manufacturing apparatus which is the vertical final polymerization tank. It is possible to reduce the apparatus price of the continuous manufacturing apparatus, and further, there is an advantage that the installation space of the apparatus can be significantly reduced.

[Brief description of drawings]

FIG. 1 is an apparatus configuration diagram showing an embodiment of the present invention.

FIG. 2 is a device configuration diagram showing another embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... 1st manufacturing apparatus main body, 2 ... Ester exchange tank, 3 ... Initial polymerization tank, 4 ... Supply nozzle, 5 ... Extraction nozzle, 6 ... Low viscosity stirring blade, 7 ... Connection pipe, 8a ... Ring tray, 8b
... Cylindrical tray, 9 ... Flow rate adjusting valve, 10 ... Volatile substance taking-out nozzle, 11 ... By-product removing nozzle, 12 ... By-product, 13 ... Raw material, 14 ... Volatile substance, 15 ... Prepolymer, 2
0 ... Stirring chamber, 21 ... Connection pipe, 22 ... Stirring blade, 23 ... Stirring shaft, 24 ... Tray, 30 ... Second manufacturing device body, 32 ... Rotating shaft, 31 ... Driving device, 42 ... Lower bearing, 38 ... L Mold ring member, 39 ... Donut-shaped stirring chamber, 37 ... Stirring member, 33 ... Treatment liquid inlet nozzle, 34 ... Treatment liquid outlet nozzle, 35 ... Volatile substance outlet nozzle, 36 ... Downcomer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takanobu Furukawa 794 Azuma Higashitoyo, Shimomatsu City, Yamaguchi Prefecture Stock company Hitachi Kasado Plant (72) Inventor Takatoshi Kinoshita 794 Higashitoyo, Higashitoyo, Yamaguchi Prefecture (72) Inventor, Kazuki Harada, Kamimatsu City, Yamaguchi Prefecture, 794, Higashitoyoi, Higashi-Toyo, Ltd., Inside the Kasado Plant, Hitachi, Ltd.

Claims (17)

[Claims] 1. A production apparatus for continuously producing a polycondensation polymer, wherein a polycondensation reaction is carried out between an oligomer and a transesterification tank for producing an oligomer by a transesterification reaction from a mixture of raw materials to produce an intermediate polymer. Intermediate polymerization is carried out by a polycondensation reaction with a first production device that is formed by arranging an initial polymerization tank in series in the vertical direction and connecting the upper column transesterification column and the lower column initial polymerization column to form an integrated structure. An apparatus for continuously producing a polycondensation polymer, comprising a vertical second production apparatus for producing a final polymer from a product. 2. The continuous manufacturing apparatus according to claim 1, wherein the raw material inlet of the upper tower of the first manufacturing apparatus is provided on the bottom side of the upper tower,
Raise the connecting pipe of the upper tower and the lower tower to the upper liquid surface of the upper tower,
The end of the connecting pipe of the lower tower is provided in the liquid in the liquid pool provided at the upper part of the lower tower, and the outlet of the processing liquid is provided at the bottom of the lower tower. Continuous manufacturing equipment. 3. The continuous production apparatus according to claim 2, wherein a flow rate adjusting valve is provided in a connecting pipe connecting the upper tower and the lower tower to control the flow rate to a predetermined value even when there is a pressure difference between the upper tower and the lower tower. An apparatus for continuously producing a polycondensation polymer, which is characterized in that 4. The continuous production apparatus according to claim 2, wherein the upper tower is provided with a low-viscosity stirring blade for uniformly stirring and mixing the inside of the tank, and the lower tower is provided with a tray having a plurality of liquid pools. Then
An apparatus for continuously producing a polycondensation polymer, which has a structure without a stirring blade. 5. The continuous manufacturing apparatus according to claim 4, wherein a plurality of trays installed in the lower tower have a circular shape having a cross-sectional shape of an L-shaped ring-shaped tray and a diameter larger than the diameter of the ring-shaped hollow portion. An apparatus for continuous production of polycondensation polymer, characterized in that a plurality of trays are alternately installed. 6. The continuous manufacturing apparatus according to claim 5, wherein a part or a plurality of cutout trays are provided on each of the inner diameter side of the L-shaped ring tray and the outer diameter side of the circular tray installed in the lower tower. An apparatus for continuously producing a polycondensation polymer, characterized in that the treatment liquid in the inside is made to flow down. 7. The continuous manufacturing apparatus according to claim 2, wherein the upper tower is provided with a low-viscosity stirring blade for uniformly stirring and mixing the inside of the tank, and the lower tower is divided into a plurality of stages in the longitudinal direction inside the main body. Then, a ring-shaped member having an L-shaped cross section was used to form a stirring chamber having a space in the center, and the stirring member that stirs each stirring chamber thoroughly was attached to a stirring shaft provided in the center of the lower tower. An apparatus for continuously producing a polycondensation polymer, characterized by: 8. The continuous production apparatus according to claim 7, wherein a connecting pipe for connecting the upper and lower stirring chambers provided in the lower tower is the liquid surface side on the upper stirring chamber side and the stirring chamber bottom is on the lower stirring chamber side. An apparatus for continuously producing a polycondensation polymer, which has a structure of connecting to a polycondensation polymer. 9. The continuous production apparatus according to claim 2, wherein the upper tower is provided with an external circulation type stirring mechanism for uniformly stirring and mixing the inside of the tank, and has a structure without a stirring blade. Continuous polycondensation polymer production equipment. 10. The continuous manufacturing apparatus according to claim 1,
The second manufacturing apparatus has an inlet and an outlet for the liquid to be treated, respectively at the upper and lower portions in the longitudinal direction of the substantially vertical cylindrical container body, and the stirring member is attached to the rotary shaft provided in the longitudinal direction inside the body. A device that rotates close to the inside of the main body, the inside of the main body is divided into a plurality of ring-shaped members, and a gap for passing volatile matter is provided between the inside of the doughnut-shaped stirring chamber and the rotation shaft. An apparatus for continuously producing a polycondensation polymer, which is provided with an outlet for volatile matter on its side surface. 11. The continuous manufacturing apparatus according to claim 10, wherein the second manufacturing apparatus forms the doughnut-shaped stirring chamber with a ring-shaped member having an L-shaped cross section, and scrapes the inner wall surface of each stirring chamber thoroughly. An apparatus for continuously producing a polycondensation polymer, wherein a frame-shaped stirring member is attached to a rotary shaft. 12. The continuous manufacturing apparatus according to claim 10, wherein the second manufacturing apparatus divides the inside of the main body into a plurality of parts by a partition plate and seals with a shaft sealing device, and a volatile matter outlet nozzle for each divided area. A continuous production apparatus for polycondensation polymers, characterized in that the pressure can be changed for each divided area by attaching the. 13. The continuous manufacturing apparatus according to claim 10, wherein in the second manufacturing apparatus, the main body is divided into upper and lower parts by partition plates, and the drive device is attached to the upper and lower parts of the main body, and different rotations are made for each divided area. An apparatus for continuously producing a polycondensation polymer, which is capable of stirring with a number. 14. A polycondensation polymer raw material is supplied to a first production apparatus by the continuous production apparatus according to any one of claims 1 to 12, and a transesterification reaction is carried out in the upper column under substantially atmospheric pressure. An oligomer is produced, and in the lower tower, a polycondensation reaction operation is performed in a reduced pressure atmosphere to obtain an initial polymerization reaction product or an intermediate polymerization reaction product having a low polymerization degree to a medium polymerization degree, and further supplying the reaction product to the second manufacturing apparatus. Then, a polycondensation reaction operation is performed in a reduced pressure atmosphere to obtain a reaction product having a high degree of polymerization, which is a continuous production method of a polycondensation polymer. 15. The continuous production apparatus according to any one of claims 1 to 12, wherein a mixture of terephthalic acid and ethylene glycol or a mixture of dimethyl terephthalate and ethylene glycol is supplied as a raw material to the first production apparatus, and the temperature is raised in the upper tower. The temperature is 200 ° C to 270 ° C, the pressure is at atmospheric pressure or under pressure, and the transesterification reaction is performed to produce bisbetahydroxyethyl terephthalate, which is then flowed down to the lower column at a temperature of 200 ° C to 300 ° C and a pressure of 13000Pa to 13 ° C.
Within a range of 3 Pa, volatile substances such as ethylene glycol are evaporated to sequentially move to a stirring chamber on the downstream side to increase the degree of polymerization,
Furthermore, it supplies to the 2nd manufacturing equipment, temperature from 260 ℃ to 300
A continuous polycondensation method of polyethylene terephthalate for increasing the degree of polymerization by performing a polycondensation reaction at a temperature of 10 kPa to 0.01 kPa at a temperature of 10 kPa to 0.01 kPa. 16. A transesterification tank for producing an oligomer by a transesterification reaction from a mixture of raw materials and an initial polymerization tank for polycondensation reaction of the oligomer to produce an intermediate polymer are vertically integrated in series. A method for continuously producing a polycondensation polymer, comprising producing a final polymer from the intermediate polymer in a vertical stirring tank. 17. The continuous manufacturing method according to claim 14, wherein the vertical stirring tank is configured by being separated from the integrated transesterification tank and initial polymerization tank.