JPH0517505A - Continuous polymerization unit and continuous polymerization using the same - Google Patents

Abstract

PURPOSE:To provide the subject unit of high production efficiency, capable of controlling molecular weight distribution and producing a high-viscosity polymer, having a polymerizer with a stock feed port in the front and a takeout port in the rear and only radially mixing ability and a second polymerizer having plural stock feed ports. CONSTITUTION:Stocks are continuously fed into (A) the first continuous polymerizer 1 of extrusion type having a stock feed port 3 in the front and a polymer takeout port 4 in the rear and equipped with an agitation mechanism 6 with only radially mixing ability, and the resulting polymer is agitatedly transported without backmixing and continuously drawn off the takeout port 4. The polymer is then fed into the second continuous polymerizer 2 having plural stock feed ports 3 along the flow direction and a polymer takeout port 5 in the rear and equipped with an agitation mechanism 6 with radially mixing ability. The resultant polymer is continuously, and agitatedly transported without backmixing and drawn off the takeout port 5, thus obtaining the final polymer in a continuous manner.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous polymerization apparatus and a continuous polymerization method, and more specifically, to control the residence time distribution of the polymer in the polymerization apparatus in continuous polymerization, thereby The present invention relates to a device capable of arbitrarily controlling a molecular weight distribution and a polymerization method using the device.

[0002]

2. Description of the Related Art Conventionally, a polymer has been produced by a batch method or a continuous method, but in either method, the molecular weight distribution is determined from the reaction engineering characteristics. Regardless of which method is used, there are few conventional polymer production apparatuses and production methods whose molecular weight distribution can be controlled, and even if there is any, devised to narrow the molecular weight distribution of the polymer. Was the most. As an apparatus and method for easily producing a polymer having a specific distribution in molecular weight, there is one described in JP-A-2-70704. However, in this method, in the latter stage of the polymerization reaction, The polymer's abrupt viscosity increase causes the polymer to wind around the stirring shaft or adhere in the reaction tank, making it difficult to stir and mix or withdraw the polymer, or it is difficult to control the degree of polymerization of the polymer. There was a problem that became. Therefore, for the synthesis of a polymer having a constant molecular weight distribution, various polymerization conditions are searched and determined, or when the desired molecular weight distribution is still not obtained, the polymer having the required molecular weight is changed by changing the reaction conditions. Was polymerized, and then they were mixed and homogenized at a required blending ratio to obtain a polymer mixture having a desired molecular weight distribution. However, even if a single type of polymer mixture is produced by this method, the batch method requires several batches, and the continuous method requires several lines, which complicates the manufacturing equipment and manufacturing process, resulting in low production efficiency. there were.

Therefore, it is an object of the present invention to provide a polymerization apparatus and a polymerization method which are excellent in controlling the molecular weight distribution, simplifying the manufacturing process, and dealing with high-viscosity polymers and have high production efficiency.

[0004]

In view of the state of the art as described above, the inventors of the present invention have conducted diligent research to find a rational and efficient method for obtaining a polymer having an arbitrary molecular weight distribution. As a result, the present invention has been completed. That is, the present invention has a polymerization raw material supply port in the front part and a polymer outlet port in the rear part with respect to the flow direction, has substantially no mixing ability in the flow direction, and has mixing ability in the radial direction. It has a first continuous polymerization device with an extruding flow equipped with a stirring mechanism, a plurality of polymerization raw material supply ports in the flow direction, and a polymer extraction port in the rear part, and has substantially no mixing ability in the flow direction. A continuous polymerization apparatus characterized by having a second continuous polymerization apparatus with an extruding flow equipped with a stirring mechanism having a mixing ability in the radial direction, and using this continuous polymerization apparatus, the polymerization raw material is first continuous It is continuously supplied from the polymerization raw material supply port provided in the polymerization apparatus, and the polymer is continuously agitated and transferred toward the polymer extraction port without back mixing, and polymerization is performed from the extraction port installed at a fixed position. Was continuously taken out, and then the polymerization raw material was continuously supplied from a plurality of polymerization raw material supply ports provided in the second continuous polymerization apparatus, and continuously and without back mixing toward the polymer extraction port. Stir the polymer,
It is intended to provide a continuous polymerization method characterized in that a polymer is taken out from a take-out port installed at a fixed position.

The present invention also has a plurality of polymerization raw material supply ports and / or a plurality of polymer outlets in the flow direction, and has substantially no mixing ability in the flow direction and a radial direction. On the other hand, a first continuous polymerization apparatus using an extruding flow equipped with a stirring mechanism having a mixing ability, a plurality of polymerization raw material supply ports in the flow direction, and a polymer extraction port in the rear part are provided, and the flow direction is substantially the same. Which has a second continuous polymerization device by an extruding flow provided with a stirring mechanism having a mixing ability in the radial direction, and a continuous polymerization device using this continuous polymerization device. The raw material is continuously supplied from at least one of the one or a plurality of polymerization raw material supply ports provided in the first continuous polymerization device, and continuously and back-mixed toward the polymer outlet. The polymer is agitated and transferred without exception, and the polymer is continuously taken out from at least one of the one or a plurality of polymer take-out ports provided in the first continuous polymerization apparatus, and then the polymerization raw material is used. Is continuously supplied from a plurality of polymerization raw material supply ports provided in the second continuous polymerization apparatus, and the polymer is continuously agitated and transferred toward the polymer extraction port without backmixing, to a predetermined position. The present invention provides a continuous polymerization method characterized in that a polymer is taken out from an installed take-out port.

Polymerization reactions capable of controlling the molecular weight distribution by the polymerization apparatus and the polymerization method of the present invention include radical polymerization reactions such as polystyrene and polycondensation reactions such as polyester and polyamide. In the present invention, the polymerization raw material supplied from the supply ports of the first and second continuous polymerization apparatuses is a monomer or a mixture thereof, a low molecular weight compound due to a reaction between monomers, that is, a prepolymer, a high molecular weight compound, etc. A homogeneous composition or a homogeneous mixture containing monomer units involved in If necessary, various powders such as dyes and pigments and polymer property improvers can be added to the polymerization raw materials supplied to the first and second continuous polymerization apparatuses.

In the present invention, the polymerization raw materials supplied to the first and second continuous polymerization devices are extruded and carried to the polymer outlet. Here, the pushing flow is a flow moving by a pressure difference between the inlet and the outlet or a conveying mechanism such as a screw, and mixing in a plane perpendicular to the flow direction is sufficient, and mixing along the flow direction ( There is virtually no back mixing). In the present invention, the use of extrusion flow is essential for improving the controllability of the molecular weight distribution. When back mixing occurs, it becomes difficult to control the molecular weight distribution of the polymer.

The first and second continuous polymerization apparatuses may basically have the same structure, but it is preferable that the first continuous polymerization apparatus has a mechanism capable of keeping the residence time long, and the second continuous polymerization apparatus is preferable. The device preferably has a forced extrusion mechanism. The stirring mechanism that satisfies the above conditions is a mechanism that does not cause back mixing used in the bulk polymerization reaction. For example, as the first continuous polymerization device, a single forward screw, a multi-stage rotating disk, or a multi-spindle is used. By using a stirring mechanism such as a positive direction screw or a multi-stage rotating disk, or a stirring mechanism such as an extruder with a uniaxial forward direction screw or a multiaxial forward direction screw as the second continuous polymerization device. It is possible to obtain (a screw having a twist in the direction of flow in normal rotation is called a forward screw).

The continuous polymerization apparatus and continuous polymerization method of the present invention will be described below with reference to the drawings. FIG. 1 is an apparatus for adjusting the molecular weight by providing one supply port 3 in the first continuous polymerization apparatus 1 and a plurality of supply ports 3 in the second continuous polymerization apparatus 2. The number of the supply ports 3 in 2 is arbitrary, but it does not make much sense if it is too large, and considering the balance with the number of stages of the stirring blades 6 and the operability of distribution of the polymerization raw material, the flow direction It is preferable that the number is 2-10. The distance between the supply ports 3 can be arbitrarily selected according to the desired molecular weight distribution. FIG. 2 is an apparatus for adjusting the molecular weight by providing a plurality of supply ports 3 in the first and second continuous polymerization apparatuses 1 and 2, and the number of supply ports 3 is the same as that described in FIG. In the continuous polymerization apparatus 1 of No. 1, it is preferable to set 2 to 30 points in the flow direction, and in the second continuous polymerization apparatus 2, it is preferable to set to 2 to 10 points. FIG. 3 shows an apparatus for adjusting the molecular weight by providing a plurality of outlets 4 in the first continuous polymerization apparatus 1 and a plurality of supply ports 3 in the second continuous polymerization apparatus 2. The number of the outlets 4 of FIG.
In the same meaning as described above for the supply port, too much is not effective and it is preferable to set 2 to 30 places in the flow direction and 2 to 10 places for the supply port 3 of the second continuous polymerization apparatus. FIG. 4 shows the first and second
1 is a device for adjusting the molecular weight by providing a plurality of supply ports 3 in the continuous polymerization apparatuses 1 and 2 and a plurality of outlets 4 in the first continuous polymerization apparatus 1. The number of the supply ports 3 is as shown in FIG. ~ 3
In the same meaning as described above, 2 to 30 places in the flow direction in the first continuous polymerization apparatus 1 and 2 to 10 in the second continuous polymerization apparatus 2
The number of outlets 4 of the first continuous polymerization apparatus 1 is also shown in FIG.
In the same meaning as described in 1 to 3, too much is not effective and it is preferable to set 2 to 30 places in the flow direction. 1 to 4 above
The first and second continuous polymerization apparatuses 1 and 2 shown in FIG.
A two-axis multi-stage rotating disk and a two-axis co-rotating screw are respectively provided as.

The supply amount distribution of the polymerization raw material from the plurality of supply ports 3 of the first or second continuous polymerization apparatus is determined by the plurality of supply ports 3 installed according to the molecular weight distribution of the desired polymer. Using any one of the supply ports and / or by a flow control valve. In the case of taking out from a plurality of taking-out ports 4, the adjustment is carried out in the same manner according to the molecular weight distribution of the intended polymer. In these apparatuses, the polymerization raw material supplied to the first continuous polymerization apparatus may be distributed and supplied to the first continuous polymerization apparatus 1 and the second continuous polymerization apparatus 2 as needed. Further, in the case of polycondensation, low molecular weight by-products such as water and alcohol are generated, and therefore a heating and extraction mechanism for distilling off these by-products is required. In the apparatus shown in the drawing, a discharge port 8 is provided as a mechanism for extracting this by-product or low molecular weight volatile matter. For heating, a heat transfer mechanism such as a heat medium jacket 7 may be provided outside the polymerization apparatus and / or inside the stirring shaft. Such a heat transfer mechanism can also be used for heat removal in cases such as radical polymerization. Provide a dedicated degassing port for distilling off low molecular weight by-products as described above, and if necessary, provide a suction port for decompression and a transfer gas inlet port for transferring the gas to be distilled off. Is also possible. The molecular weight distribution of the polymerization product can be controlled by controlling the temperature in the tank, the pressure, the balance of the supply amount or the balance of the withdrawal amount of the polymerization product, and also by changing the rotation speed of the stirring and transferring mechanism.

[0011]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The parts in the examples are parts by weight. The average residence time is the residence time of the total amount of the polymerization raw material supplied from each supply port with respect to the total amount of the polymer in the polymerization apparatus.

Example 1 The tank volume was 40 liters, the total length in the reaction tank was 800 mm, and the inner diameter was 250 m.
m, a first continuous polymerization apparatus I having a degassing port at the upper position of the outlet of the end of the reaction tank and having a biaxial rotating disk as a stirring blade, the internal volume of the tank is 1 liter, the total length of the reaction tank is 500 mm,
Second continuous polymerization device II with inner diameter of 50 mm and inlets of polymerization device at three positions of 50 mm, 350 mm, and 450 mm from the end face of the device, and equipped with twin co-rotating screws as stirring blades It was possible to produce a polyester polymer having a desired specific molecular weight distribution. In the polymerization of the present polyester, a reaction tank III (volume of 40 liters) for performing a pre-reaction and a mixing device IV were provided before the first continuous polymerization device I.

In the polyester polymerization reaction, 29.4 parts of adipic acid as an acid component, 70.6 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane as an alcohol component, and antimony oxide as a reaction catalyst. 0.1 part was continuously supplied to the reaction tank III so that the total amount was 11.5 kg / hr, and the esterification reaction was continuously carried out.

The reaction temperature of this esterification step is 250 ° C.,
The pressure was 220 mmHg and the average residence time was 2 hours. This was continuously led to the mixing apparatus IV, and the esterification reaction product 10
Trimellitic anhydride was continuously supplied and mixed at a flow rate ratio of 10 parts to 0 parts to prepare a polymerization raw material for the first continuous polymerization apparatus I. In the subsequent reaction in the high viscosity region, the polymerization raw materials uniformly mixed in the mixing apparatus IV were supplied to the first continuous polymerization apparatus I. During this period, the temperature of the first continuous polymerization apparatus I was changed to
The pressure inside the tank was maintained at 220 ° C and 50 mmHg. The average residence time was 1.5 hours. Then, the polymer obtained in the first continuous polymerization apparatus I, from the supply port installed at the position of 50 mm and 450 mm from the inlet end device end surface of the second continuous polymerization apparatus II,
The supply was performed so that the supply weight ratio was 90:10. During this period, the temperature of the second continuous polymerization apparatus II was kept at 210 ° C. and the pressure in the tank was kept at normal pressure. The average residence time was 5 minutes.

Thus, the dispersion index (ratio between the weight average molecular weight and the number average molecular weight) showing the broadening of the molecular weight distribution with a softening point of 120 ° C., a number average molecular weight of 4100 and a weight average molecular weight of 193,000.
A polyester resin having a target molecular weight distribution of 47 was obtained.

Example 2 The tank volume was 40 liters, the total length in the reaction tank was 800 mm, and the inner diameter was 250 m.
m, 10 polymerization material supply ports are provided at the top every 50 mm from the inlet, a degassing port is provided at the upper position of the outlet of the reaction tank, and a biaxial rotating disk is provided as a stirring blade. Continuous polymerization apparatus V, tank internal volume 1 liter, reaction tank total length 50
0 mm, inner diameter 50 mm, 50 mm from inlet device end face, 350 mm, 45
By using a second continuous polymerization apparatus VI equipped with polymerization raw material supply ports at three positions of 0 mm and equipped with biaxial co-rotating screws as stirring blades, a desired specific molecular weight distribution can be obtained. A polyester polymer could be produced. As in Example 1, a reaction vessel VII (volume of 40 liters) for carrying out a pre-reaction and a mixing apparatus VIII were provided before the first continuous polymerization apparatus V.

In the present polyester polymerization reaction, the same acid component, alcohol component, and reaction catalyst as in Example 1 were mixed at the same composition ratio and continuously supplied to the reaction vessel VII at the same flow rate as in Example 1 to continuously produce the same. Was esterified. The reaction temperature of this esterification process is 250 ° C, the pressure is 220 mmHg,
The average residence time was 2 hours. This is continuously introduced into the mixing device VIII, trimellitic anhydride is continuously supplied and mixed at a flow rate ratio of 10 parts to 100 parts of the esterification reaction product, and the polymerization raw material of the first continuous polymerization device V is supplied. And The polymerization raw material is supplied from a supply port near the entrance of the first continuous polymerization apparatus V and a supply port installed at a position 400 mm from the entrance.
It was supplied so that the supply weight ratio was 70:30. During this period, the temperature of the first continuous polymerization apparatus V was 230 ° C and the pressure in the tank was 50 mmHg.
Kept at. The average residence time was 1.5 hours. Thereafter, the polymer obtained in the first continuous polymerization apparatus V was supplied to the second continuous polymerization apparatus VI at the inlets 50 mm and 450 mm from the end face of the apparatus, and the supply weight ratio was 80: It was supplied to 20. During this period, the temperature of the second continuous polymerization apparatus VI was kept at 215 ° C. and the pressure inside the tank was kept at normal pressure. The average residence time was 5 minutes.

Thus, a polyester resin having a desired softening point of 118 ° C., a number average molecular weight of 4000, a weight average molecular weight of 332000 and a dispersion index of 83 showing the spread of the molecular weight distribution and having a desired molecular weight distribution was obtained.

[0019]

Industrial Applicability According to the present invention, there are provided a polymerization apparatus and a polymerization method which are excellent in controlling the molecular weight distribution, simplifying the manufacturing process, and dealing with high-viscosity polymers and have high production efficiency.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a continuous polymerization apparatus of the present invention.

FIG. 2 is a diagram showing another example of the continuous polymerization apparatus of the present invention.

FIG. 3 is a view showing still another embodiment of the continuous polymerization apparatus of the present invention.

FIG. 4 is a view showing still another embodiment of the continuous polymerization apparatus of the present invention.

[Explanation of symbols]

1 First continuous polymerization equipment 2 Second continuous polymerization equipment 3 Polymerization material supply port 4 Polymer outlet 5 Polymerization product outlet 6 stirring blades 7 Heat medium jacket 8 By-product or low molecular weight volatile matter outlet 9 Transfer pump

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[Procedure amendment]

[Submission date] September 2, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

In the polyester polymerization reaction, 29.4 parts of adipic acid as an acid component, 70.6 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane as an alcohol component, and antimony oxide as a reaction catalyst. 0.1 part was continuously supplied to the reaction tank III so that the total amount was 12.1 kg / Hr, and the esterification reaction was continuously carried out.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The reaction temperature of this esterification step is 250 ° C.,
The pressure was 220 mmHg and the average residence time was 2 hours. This was continuously led to the mixing apparatus IV, and the esterification reaction product 10
Trimellitic anhydride was continuously supplied and mixed in a weight ratio of 10 parts to 0 parts to prepare a polymerization raw material for the first continuous polymerization apparatus I. In the subsequent reaction in the high viscosity region, the polymerization raw materials uniformly mixed in the mixing apparatus IV were supplied to the first continuous polymerization apparatus I. During this period, the temperature of the first continuous polymerization apparatus I was changed to
The pressure inside the tank was maintained at 220 ° C and 50 mmHg. The average residence time was 1.5 hours. Then, the polymer obtained in the first continuous polymerization apparatus I, from the supply port installed at the position of 50 mm and 450 mm from the inlet end device end surface of the second continuous polymerization apparatus II,
The supply was performed so that the supply weight ratio was 90:10. During this period, the temperature of the second continuous polymerization apparatus II was kept at 210 ° C. and the pressure in the tank was kept at normal pressure. The average residence time was 5 minutes.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

In the present polyester polymerization reaction, the same acid component, alcohol component, and reaction catalyst as in Example 1 were mixed at the same composition ratio and continuously supplied to the reaction vessel VII at the same flow rate as in Example 1 to continuously produce the same. Was esterified. The reaction temperature of this esterification process is 250 ° C, the pressure is 220 mmHg,
The average residence time was 2 hours. This is continuously introduced into the mixer VIII, trimellitic anhydride is continuously supplied and mixed in a weight ratio of 10 parts to 100 parts of the esterification reaction product, and the mixture is mixed to prepare the polymerization raw material of the first continuous polymerization device V. And The polymerization raw material is supplied from a supply port near the entrance of the first continuous polymerization apparatus V and a supply port installed at a position 400 mm from the entrance.
It was supplied so that the supply weight ratio was 70:30. During this period, the temperature of the first continuous polymerization apparatus V was 230 ° C and the pressure in the tank was 50 mmHg.
Kept at. The average residence time was 1.5 hours. Thereafter, the polymer obtained in the first continuous polymerization apparatus V was supplied to the second continuous polymerization apparatus VI at the inlets 50 mm and 450 mm from the end face of the apparatus, and the supply weight ratio was 80: It was supplied to 20. During this period, the temperature of the second continuous polymerization apparatus VI was kept at 215 ° C. and the pressure inside the tank was kept at normal pressure. The average residence time was 5 minutes.

Claims (4)

[Claims] 1. A polymerization raw material supply port is provided at a front part and a polymer extraction port is provided at a rear part with respect to a flow direction, and there is substantially no mixing ability in the flow direction but a mixing ability in the radial direction. It has a first continuous polymerization device with an extruding flow equipped with a stirring mechanism, a plurality of polymerization raw material supply ports in the flow direction, and a polymer extraction port in the rear part, and has substantially no mixing ability in the flow direction. A continuous polymerization apparatus having a second continuous polymerization apparatus with an extruding flow provided with a stirring mechanism having a mixing ability in the radial direction. 2. A plurality of polymerization raw material supply ports and / or a plurality of polymer outlets are provided in the flow direction, and there is substantially no mixing ability in the flow direction, and mixing is performed in the radial direction. A first continuous polymerization device by an extrusion flow equipped with a stirring mechanism having a capability, a plurality of polymerization raw material supply ports in the flow direction, and a polymer extraction port in the rear part, and substantially mixing in the flow direction A continuous polymerization apparatus having a second continuous polymerization apparatus with an extruding flow, which has a stirring mechanism having a mixing ability in the radial direction with no ability. 3. The continuous polymerization apparatus according to claim 1, wherein the polymerization raw material is continuously supplied from a polymerization raw material supply port provided in the first continuous polymerization apparatus, and continuously toward a polymer outlet. The polymer is agitated and transferred without back mixing, and the polymer is continuously taken out from the take-out port installed at a fixed position, and then the polymerization raw material is supplied to a plurality of polymerization raw materials provided in the second continuous polymerization apparatus. Continuous polymerization characterized by continuously supplying from the mouth, continuously and agitating and transferring the polymer toward the polymer take-out port, and taking out the polymer from the take-out port installed at a fixed position. Method. 4. The continuous polymerization apparatus according to claim 2, wherein the polymerization raw material is continuously supplied from at least one of the one or more polymerization raw material supply ports provided in the first continuous polymerization apparatus. And continuously and agitate and transfer the polymer toward the polymer outlet without back mixing,
The polymer is continuously taken out from at least one of the one or more polymer outlets provided in the first continuous polymerization apparatus, and then the polymerization raw material is provided in the second continuous polymerization apparatus. Continuously supplied from the plurality of polymerization raw material supply ports, the polymer is continuously agitated and transferred toward the polymer extraction port without back mixing, and the polymer is extracted from the extraction port installed at a fixed position. A continuous polymerization method characterized by taking out.