JPWO2015141501A1 - Polycondensation reactive polymer and production apparatus thereof - Google Patents

Abstract

Provided is a method for producing a polycondensation-reactive polymer capable of maintaining high quality of the polycondensation-reactive polymer. A polymerizer for producing a polycondensation-reactive polymer comprising a casing, a guide provided in the casing, and a polymer outlet connected to the casing and provided below the polymer outlet. A step of supplying a prepolymer, and a step of polymerizing the molten prepolymer by allowing the molten prepolymer to flow down while contacting the surface of the guide, thereby producing a polycondensation reactive polymer. In the production method, the projected area of the portion where the condensation polymerization reactive polymer flows down in the taper-shaped lower portion of the casing is large, or the portion where the condensation polymerization-reactive polymer flows down on the liquid level of the stay in the taper-shaped lower portion of the casing The manufacturing method is controlled so as to include a large amount.

Description

  The present invention relates to a method for producing a polycondensation reactive polymer and an apparatus for producing the same.

  Polycondensation-reactive polymers are used in fields with great demand among engineer plastics, and typical examples include polycarbonate, polyamide, and polyester resins represented by PET bottles. For example, aromatic polycarbonate is an engineering plastic having excellent mechanical strength such as transparency, heat resistance and impact strength, and is widely used in industrial applications such as optical disks, electrical and electronic fields, and automobiles.

  Conventionally, various polymerization apparatuses for producing an aromatic polycarbonate by a transesterification method are known. However, since the viscosity of polycarbonate increases with polymerization, if an attempt is made to use a polymerization vessel that requires mechanical stirring, mechanical stirring becomes difficult when the degree of polymerization increases and the viscosity increases. Therefore, such a polymerization vessel has a limitation in the degree of polymerization of the polycarbonate that can be produced, and it has been difficult to produce a high-molecular-weight aromatic polycarbonate widely used for sheet applications.

  As a polymerization apparatus that does not require mechanical stirring, a guide contact flow type polymerization apparatus that polymerizes a molten prepolymer along a guide such as a wire while dropping by its own weight is known. When such a polymerization apparatus is used, the problem that stirring cannot be performed with polymerization is solved, and an aromatic monohydroxy compound (for example, phenol) as a by-product is efficiently extracted from the surface of the melt. A molecular weight aromatic polycarbonate can be produced. For example, Patent Document 1 describes a method for producing a polycondensation reactive polymer using a polymerization vessel in which a wire guide is installed at a specific interval with respect to the width of a molten prepolymer mass. According to this production method, a high-quality polycondensation reactive polymer can be produced efficiently at a high polymerization rate.

International Publication No. 2012/056903

  In the guide contact flow type polymerization apparatus, the polymer dropped from the wire guide is at the bottom of the polymerization vessel (for example, in the region between the inert gas supply port 9 and the polymer discharge port 7 in FIG. 1 of Patent Document 1). It stays until it flows out from the outlet. The amount of the polymer flowing down and the amount discharged are controlled to be approximately the same, but may increase or decrease somewhat while the operation is continued, and the liquid level of the stay may rise and fall. A part of the relatively high-viscosity polymer that was in contact with the upper wall surface of the inverted conical bottom when the liquid level was raised remains on the wall surface even after the liquid level has been lowered. When the remaining polymer is present in the flow path of the flowing polymer, the polymer is pushed away by the flowing polymer and merges with the retained material, so that there is no problem.

  However, when the remaining polymer is attached to the wall surface that is not the flow path of the flowing polymer, it remains without being pushed away by the flowing polymer, and is exposed to the ambient atmosphere or receives a heat history. It becomes easy. Then, when the liquid level of the staying material rises again, the remaining polymer is mixed with the staying material, but may deteriorate while being exposed to the ambient atmosphere or receiving a heat history. In addition, they are mixed with stagnants, which causes the quality of the resulting resin product to deteriorate.

  Conventionally, when the polymerization vessel is small and the internal structure is simple, it is easy to design the internal structure that avoids the remaining portion. Such a design includes, for example, simply and evenly installing vertical wires extending in the vertical direction. However, when the polymer is actually produced industrially, the polymerization vessel becomes large, and the structure inside the polymerization vessel becomes complicated due to problems in manufacturing and strength. For example, it is necessary to install the vertical wire by dividing it into several blocks. As a result, since the structure of the vertical wire block has a great influence on the flow path of the polymer falling from the wire, it has become necessary to have a structure that does not generate a remaining portion of the polymer.

  The present invention has been made to solve the above-mentioned problems found by the present inventors. The object of the present invention is to provide a method for producing a polycondensation-reactive polymer capable of maintaining high quality of the polycondensation-reactive polymer and its It is to provide a manufacturing apparatus.

The inventors of the present invention have made extensive studies to achieve the above object, and have completed the present invention. That is, the present invention is as described in [1] to [13] below.
[1] The following steps (I) and (II):
(I) A polymerization vessel for producing a polycondensation reactive polymer, comprising a casing, a guide provided in the casing, and a polymer outlet connected to the casing and provided below the casing. Supplying molten prepolymer to the vessel; and
(II) a step of allowing the molten prepolymer to flow down while contacting the surface of the guide to polymerize the molten prepolymer, thereby producing the condensation polymerization reactive polymer;
A method for producing a condensation-polymerization reactive polymer having
The casing includes a cylindrical upper portion having a lower end peripheral portion having a diameter larger than a diameter of the upper end peripheral portion of the polymer outlet, the lower end peripheral portion of the cylindrical upper portion, and the upper end peripheral portion of the polymer outlet. And a tapered lower portion having a tapered wall extending from the lower edge periphery to the upper edge periphery, and the casing, the guide, and the polymer outlet are dropped from the guide The polycondensation reactive polymer is arranged to flow down to the polymer outlet along the inner surface of the tapered wall while staying in the tapered lower part,
The diameter of the cylindrical upper part is 0.90 m or more and 10 m or less,
In a virtual outermost peripheral portion where the condensation polymerization reactive polymer flows down in the tapered lower part, a projected area S1 from above in a vertical direction of the portion where the condensation polymerization reactive polymer flows down, and the condensation polymerization reactive polymer includes A manufacturing method in which a projected area S2 from above in a vertical direction of a portion that does not flow down satisfies a condition represented by the following formula (1).
S1 / (S1 + S2)> 0.60 (1)
[2] The manufacturing method according to [1], wherein the projected area S1 and the projected area S2 satisfy a condition represented by the following formula (1A).
S1 / (S1 + S2)> 0.85 (1A)
[3] The manufacturing method according to [1], wherein the projected area S1 and the projected area S2 satisfy a condition represented by the following formula (1B).
S1 / (S1 + S2)> 0.95 (1B)
[4] Any of [1] to [3], wherein the guide is a wire guide including a plurality of vertical wires, and a stable production rate of the condensation polymerization reactive polymer is 5 kg / (hr · 100 mm) or more. The manufacturing method as described in any one.
[5] The following steps (I) and (II):
(I) A polymerization vessel for producing a polycondensation reactive polymer, comprising a casing, a guide provided in the casing, and a polymer outlet connected to the casing and provided below the casing. Supplying molten prepolymer to the vessel; and
(II) a step of allowing the molten prepolymer to flow down while contacting the surface of the guide to polymerize the molten prepolymer, thereby producing the condensation polymerization reactive polymer;
A method for producing a condensation-polymerization reactive polymer having
The casing includes a cylindrical upper portion having a lower end peripheral portion having a diameter larger than a diameter of the upper end peripheral portion of the polymer outlet, the lower end peripheral portion of the cylindrical upper portion, and the upper end peripheral portion of the polymer outlet. And a tapered lower portion having a tapered wall extending from the lower edge periphery to the upper edge periphery, and the casing, the guide, and the polymer outlet are dropped from the guide The polycondensation reactive polymer is disposed so as to flow down to the polymer outlet along the inner surface of the tapered wall while staying in the tapered lower part,
In a circular portion formed by contacting the liquid surface of the condensation polymerization reactive polymer staying in the tapered lower portion and the inner surface of the tapered wall, the total length L0 of the circumference, and the condensation polymerization of the circumference The manufacturing method of changing the said liquid level in the range which the length L1 of the part which contacts the part which a reactive polymer flows down substantially satisfies the conditions represented by following formula (2).
L1 / L0> 0.90 (2)
[6] The manufacturing method according to [5], wherein the liquid level is changed within a range in which the total length L0 and the length L1 satisfy a condition represented by the following formula (2A).
L1 / L0 = 1.00 (2A)
[7]
The tapered lower portion further has a tapered upper portion, a tapered lower portion, and a cylindrical middle portion sandwiched between them,
In the portion connecting the tapered upper portion and the cylindrical middle portion, there is no portion where the condensation polymerization reactive polymer does not flow down, and the liquid level of the condensation polymerization reactive polymer staying in the tapered lower portion Is controlled to exist in the cylindrical middle portion, [1] to [6].
[8] The production method according to any one of [1] to [7], wherein a residence time of the condensation polymerization reactive polymer staying in the tapered lower part is within 3 hours.
[9] The guide is a wire guide, and the polycondensation reactive polymer drops the wire guide while forming a planar fluid by contacting and integrating the different wire guides with each other. , [1] to [8] A method for producing a condensation-polymerizable reactive polymer according to any one of [8].
[10] The production method according to any one of [1] to [9], wherein the condensation polymerization-reactive polymer is an aromatic polycarbonate.
[11] An apparatus for producing a polycondensation reactive polymer comprising a polymerization vessel for producing the polycondensation reactive polymer,
The polymerizer is a casing, a guide provided in the casing, and a guide for polymerizing the molten prepolymer by bringing the molten prepolymer into contact with the surface of the casing, and connected to the casing. With a polymer outlet provided below,
The casing includes a cylindrical upper portion having a lower end peripheral portion having a diameter larger than a diameter of the upper end peripheral portion of the polymer outlet, the lower end peripheral portion of the cylindrical upper portion, and the upper end peripheral portion of the polymer outlet. And a tapered lower portion having a tapered wall extending from the lower edge periphery to the upper edge periphery, and the casing, the guide, and the polymer outlet are dropped from the guide The polycondensation reactive polymer is arranged to flow down to the polymer outlet along the inner surface of the tapered wall while staying in the tapered lower part,
In a virtual outermost peripheral portion where the condensation polymerization reactive polymer flows down in the tapered lower part, a projected area S1 from above in a vertical direction of the portion where the condensation polymerization reactive polymer flows down, and the condensation polymerization reactive polymer includes The manufacturing apparatus in which the projected area S2 from above in the vertical direction of the portion that does not flow down satisfies the condition represented by the following formula (1).
S1 / (S1 + S2)> 0.60 (1)
[12] The manufacturing apparatus according to [11], wherein the tapered lower portion further includes a tapered upper portion, a tapered lower portion, and a cylindrical middle portion sandwiched therebetween.
[13] The polycondensation reactive polymer that stays in the tapered lower portion without a portion where the polycondensation reactive polymer does not flow down in a portion connecting the tapered upper portion and the cylindrical middle portion. The manufacturing apparatus according to [12], wherein the liquid level can be controlled to be present in the cylindrical middle portion.
[14] The production apparatus according to any one of [11] to [13], wherein the polycondensation reactive polymer is an aromatic polycarbonate.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the condensation polymerization reactive polymer which can maintain the quality of a condensation polymerization reactive polymer highly, and its manufacturing apparatus can be provided.

It is the schematic which shows an example of the superposition | polymerization apparatus used by embodiment of this invention. It is the schematic which shows an example of the superposition | polymerization apparatus used by embodiment of this invention, (A) is the schematic of a polymerization device, (B) is the schematic which shows the JJ cross section of the polymerization device, (C) is an enlarged view showing the wire guide of (B), and (D) is a schematic view showing a part of the wire guide of (C). It is the schematic which shows an example of the superposition | polymerization apparatus used by the comparative examples 3 and 4, (A) is the schematic of a polymerization device, (B) is the schematic which shows the KK cross section of the polymerization device, (C) is an enlarged view showing the wire guide of (B), and (D) is a schematic view showing a part of the wire guide of (C). It is the schematic which shows another example of the superposition | polymerization apparatus used by embodiment of this invention. (A) And (B) is the schematic which shows arrangement | positioning of the wire guide in the superposition | polymerization apparatus used in the Example of this invention.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is limited to the following embodiment. It is not a thing. The present invention can be variously modified without departing from the gist thereof. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. Further, in this specification, “diameter” and “diameter” mean “inner diameter” unless otherwise specified, when both the inner diameter and the outer diameter can be interpreted.

The method for producing a polycondensation reactive polymer of the present embodiment includes the following steps (I) and (II): (I) a polymerizer for producing a polycondensation reactive polymer comprising a casing and a casing. Supplying a molten prepolymer to a polymerization vessel comprising a provided guide and a polymer outlet connected to the casing and provided below the casing; and (II) bringing the molten prepolymer into contact with the surface of the guide. The molten prepolymer is allowed to flow down while polymerizing the molten prepolymer, thereby producing a polycondensation reactive polymer, wherein the casing has a diameter larger than that of the upper peripheral edge of the polymer outlet. A cylindrical upper part having a lower peripheral edge having a larger diameter, and a lower peripheral part of the cylindrical upper part and an upper peripheral part of the polymer outlet, and from the lower peripheral part to the upper peripheral part. The casing, the guide and the polymer outlet are tapered while the condensation polymerization reactive polymer falling from the guide stays in the tapered lower part. It is arranged so as to flow down to the polymer discharge port along the inner surface of the wall, and the diameter of the cylindrical upper part is 0.90 m or more and 10 m or less, and the virtual outermost circumference where the condensation polymerization reactive polymer flows down in the tapered lower part Within the portion, the projected area S1 from above in the vertical direction of the portion where the condensation polymerization reactive polymer flows and the projected area S2 from above in the portion where the condensation polymerization reactive polymer does not flow are expressed by the following formula (1). It satisfies the condition represented by
S1 / (S1 + S2)> 0.60 (1)

In addition, the method for producing a condensation polymerization reactive polymer according to the present embodiment includes the following steps (I) and (II): (I) a polymerization vessel for producing a condensation polymerization reactive polymer, a casing, and the casing thereof A step of supplying a molten prepolymer to a polymerization vessel comprising a guide provided therein and a polymer discharge port connected to the casing and provided therebelow; and (II) a molten prepolymer on the surface of the guide A method for producing a polycondensation-reactive polymer comprising a step of polymerizing the molten prepolymer by flowing down while contacting, thereby producing a polycondensation-reactive polymer, wherein the casing is provided at the upper peripheral edge of the polymer outlet. A cylindrical upper portion having a lower end peripheral portion having a diameter larger than the diameter, and a lower end peripheral portion of the cylindrical upper portion and an upper end peripheral portion of the polymer discharge port, and the lower end peripheral portion to the upper end peripheral portion A taper-like lower part having a taper-like wall extending toward the taper, and the above-mentioned casing, guide, and polymer discharge port are tapered while the condensation polymerization reactive polymer falling from the guide stays in the taper-like lower part. The circular shape is formed by contacting the liquid surface of the condensation polymerization reactive polymer staying in the tapered lower portion and the inner surface of the tapered wall along the inner surface of the tapered wall. In the portion, the range where the total length L0 of the circumference and the length L1 of the portion of the circumference that substantially contacts with the portion where the condensation polymerization reactive polymer flows down satisfies the condition represented by the following formula (2) Thus, the liquid level is changed.
L1 / L0> 0.90 (2)

  The polycondensation-reactive polymer in the present embodiment is a polymer produced by a reaction that proceeds between functional groups between two molecules, a low molecular weight substance is released, and a polymerization proceeds, and specifically, a polycarbonate. Resins, polyamide resins, polyesters and the like can be mentioned. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and the like. A typical example of the polycarbonate resin is an aromatic polycarbonate obtained by reacting an aromatic hydroxy compound with diaryl carbonate.

  A typical example of the polycarbonate resin in the present embodiment is an aromatic polycarbonate obtained by reacting an aromatic hydroxy compound with diaryl carbonate.

  An aromatic dihydroxy compound may be used individually by 1 type, or may be used in combination of 2 or more type. A typical example of the aromatic dihydroxy compound is bisphenol A. When bisphenol A is used simultaneously with other aromatic dihydroxy compounds, it is preferable to use bisphenol A in a proportion of 85 mol% or more based on the total amount of the aromatic dihydroxy compounds. These aromatic dihydroxy compounds preferably have a small content of chlorine atom and alkali or alkaline earth metal, and are preferably substantially free (100 ppb or less) if possible.

  As the diaryl carbonate, for example, symmetric diaryl carbonates such as unsubstituted diphenyl carbonate and lower alkyl-substituted diphenyl carbonates such as ditolyl carbonate and di-t-butylphenyl carbonate are preferable, and diphenyl carbonate is more preferable. These diaryl carbonates may be used individually by 1 type, and may be used in combination of 2 or more type. These diaryl carbonates preferably have a low content of chlorine atoms and alkalis or alkaline earth metals. If possible, these diaryl carbonates do not substantially contain them, that is, their content is preferably 10 ppb or less.

  The use ratio (feed ratio) of the aromatic dihydroxy compound and diaryl carbonate varies depending on the kind of the aromatic dihydroxy compound and diaryl carbonate used, the target molecular weight, the hydroxyl group terminal ratio, the polymerization conditions, and the like, and is not particularly limited. The diaryl carbonate is preferably 0.9 to 2.5 mol, more preferably 0.95 to 2.0 mol, still more preferably 0.98 to 1.5 mol with respect to 1 mol of the aromatic dihydroxy compound. Used. Moreover, in this embodiment, you may use together aromatic monohydroxy compounds, such as a phenol, t-butylphenol, and cumylphenol, for terminal conversion and molecular weight adjustment.

  Moreover, in this embodiment, you may use a polyfunctional compound together in order to introduce | transduce a branched structure into a condensation-polymerization reactive polymer in the range which does not impair the objective achievement of this invention. For example, when producing a branched polymer of an aromatic carbonate, the amount of a polyfunctional compound such as a trivalent aromatic trihydroxy compound used is 0.2 to 1.0 mol% with respect to 100 mol% of the aromatic dihydroxy compound. Is more preferable, 0.2 to 0.9 mol% is more preferable, and 0.3 to 0.8 mol% is particularly preferable.

The polycondensation-reactive polymer can be produced without adding a polymerization catalyst, but is performed in the presence of a catalyst as necessary in order to increase the polymerization rate. When using a catalyst, only 1 type of catalyst may be used and it may be used in combination of 2 or more type. The amount of the catalyst used is, for example, usually 1.0 × 10 ⁻⁸ to 1.0 part by mass with respect to 100 parts by mass of the aromatic dihydroxy compound as a raw material when an aromatic polycarbonate is produced using an aromatic dihydroxy compound as a raw material. Preferably, it is selected in the range of 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻¹ parts by mass.

  When the polycondensation reactive polymer is an aromatic polycarbonate, the number average molecular weight is preferably in the range of 500 to 100,000, more preferably in the range of 2000 to 30000. The number average molecular weight can be measured using gel permeation chromatography (GPC).

  In the present embodiment, the “melted prepolymer” means a melt during polymerization. For example, when the polycondensation-reactive polymer is an aromatic polycarbonate, the “melt prepolymer” is obtained from an aromatic dihydroxy compound and diaryl carbonate, and is lower than the aromatic polycarbonate having the desired number average molecular weight. It means a melt in the middle of polymerization having a molecular weight. That is, it may refer to a polymerization raw material introduced into the polymerization vessel, or may refer to a polymer whose molecular weight is increased by a certain degree of polymerization reaction in the polymerization vessel. The molten prepolymer may be an oligomer. The reaction of the mixture of the aromatic dihydroxy compound and diaryl carbonate is progressed only by heating and melting, so that these mixtures are substantially molten prepolymers. The number average molecular weight of the melted prepolymer used in the present embodiment may be any as long as it is melted at the polymerization temperature, and also varies depending on its chemical structure. Usually, the number average molecular weight is in the range of 500 or more and less than 100,000, preferably 500 or more and less than 10,000, and more preferably 1000 or more and less than 8,000. Moreover, the melted prepolymer used as the polymerization raw material of the present embodiment may be obtained by any known method.

  FIG. 1 is a schematic diagram illustrating an example of a polymerization apparatus according to the present embodiment. The polymerization apparatus includes a polymerization vessel 100. The polymerization vessel 100 drops the polymerization raw material while making it contact with a wire guide for producing a polycondensation reactive polymer (hereinafter simply referred to as “wire guide”), which is an example of a guide. It is a guide contact drop polymerizer capable of performing The polymerization vessel 100 includes a raw material supply port 1, a raw material supply zone 3 that communicates with the raw material supply port 1, and a guide contact drop polymerization reaction zone 5 that is located below the raw material supply zone 3 and communicates with the raw material supply zone 3. And a polymer outlet 7 located below the guide contact drop polymerization reaction zone 5, and each of these zones is surrounded by a casing 13. A wire guide 4 is installed in the reaction zone 5. Above the wire guide 4, there is provided a distribution plate 2 for distributing the molten prepolymer as a polymerization raw material so that it can be supplied to the entire wire guide 4. The distribution plate 2 is formed with polymer supply holes 12 which are holes for transferring the molten prepolymer on the distribution plate 2 to the wire guide 4. The casing 13 includes a cylindrical upper portion 13a having a lower end peripheral portion 13e having a diameter larger than that of the upper end peripheral portion 7a of the polymer discharge port 7, a lower end peripheral portion 13e of the upper portion 13a, and an upper end peripheral portion 7a of the polymer discharge port 7. And a tapered lower portion 13c having a tapered wall extending from the lower end peripheral portion 13e toward the upper end peripheral portion 7a. The wire guide 4 is a combination of a plurality of vertical wires 10 extending in the vertical direction and a fixing wire 11 extending in the horizontal direction.

  The fixing wire 11 holds the vertical wire 10 structurally, and can be omitted. Moreover, although the space | interval between adjacent fixing wires when using two or more fixing wires 11 can be selected arbitrarily, Preferably they are 30 mm or more and 1000 mm or less, More preferably, they are 40 mm or more and 200 mm or less.

  An example of a guide contact drop polymerizer (hereinafter sometimes simply referred to as “polymerizer”) and a production method using the same will be described in detail with reference to FIG. In the following description, the case where the condensation polymerization reactive polymer is an aromatic polycarbonate will be described. However, the present invention is not limited to those described below.

  The molten prepolymer is supplied from the raw material supply port 1 to the polymerization vessel 100. The supplied molten prepolymer is transferred to the raw material supply zone 3 above the distribution plate 2, and through the polymer supply hole 12 formed in the distribution plate 2, the guide contact drop polymerization reaction zone 5 in which the wire guide 4 is held. It is transferred to. The molten prepolymer is supplied to the upper end of the wire guide 4 and falls by its own weight while contacting along the vertical wire 10 of the wire guide 4. A monohydroxy compound (for example, phenol) produced as a by-product in the polymerization reaction during the dropping is extracted from the vacuum vent port 6, whereby the polymerization reaction proceeds to produce an aromatic polycarbonate. The aromatic polycarbonate is extracted by a discharge pump 8 via a polymer discharge port 7 located at the bottom.

  When a molten prepolymer and an aromatic polycarbonate produced therefrom (hereinafter referred to as “molten prepolymer or the like”) fall by its own weight while contacting one wire guide 4, at least one of the molten prepolymer or the like It is preferable that the portions come into contact with and gather with a molten prepolymer that falls while contacting the adjacent vertical wire 10 to form an integrated mass of the molten prepolymer or the like. Then, as the contact / collection of the molten prepolymer or the like between the plurality of vertical wires 10 spreads over almost the entire surface of the wire guide 4, a lump of the molten prepolymer or the like moves along the individual vertical wires 10. Instead of a “linear” drop, the wire guide 4 falls while exhibiting a “planar” appearance. Here, the mass of the melted prepolymer or the like “has a planar appearance” means that the mass of the melted prepolymer or the like straddles the plurality of vertical wires 10 and is parallel to the parallel arrangement direction of the vertical wires 10. This refers to the state of a vertical flat plate shape. That is, the molten prepolymer lump falls down the wire guide 4 while forming a planar fluid, and is converted into an aromatic polycarbonate.

  It is particularly preferable in this embodiment to use a polymerization vessel in which vertical wires are arranged so as to form this planar fluid. When producing aromatic polycarbonate of the same molecular weight at the same temperature and the same degree of vacuum, it is better to use a polymerizer that has a structure in which a lump of molten prepolymer falls in a plane rather than a linear shape. The mass flow rate per unit cross-sectional area increases. As a result, the density of the aromatic polycarbonate falling on the tapered lower portion 13c of the polymerization vessel increases. Moreover, since the amount of aromatic polycarbonate per unit time falling to the taper-shaped lower portion 13c increases when dropping in a planar shape, the cleaning effect by the aromatic polycarbonate of the tapered lower portion 13c portion is further enhanced. As the production rate of the aromatic polycarbonate, the stable production rate (kg / (hr · 100 mm)) is preferably 3 kg / (hr · 100 mm) or more, more preferably 5 kg / (hr · 100 mm) or more. It is preferably 10 kg / (hr · 100 mm) or more. Here, the “stable production rate” is a production amount of a polycondensation reactive polymer (aromatic polycarbonate) per 100 mm in a horizontal direction in a wire guide having a plurality of vertical wires per unit time. The above-mentioned production amount at the upper limit that can be stably produced. The unit is kg / (hr · 100 mm). Whether or not the aromatic polycarbonate has been stably produced is determined by whether or not the number average molecular weight (Mn) of the obtained aromatic polycarbonate is within ± 5% of the target value. If Mn is within ± 5% of the target value, it can be said that aromatic polycarbonate could be stably produced.

  In this case, when the molten prepolymers between the plurality of vertical wires 10 supplied via the polymer supply holes 12 are brought into contact with each other and gathered, a horizontal fall state is caused by the interaction of the molten prepolymers in the horizontal direction. Can be obtained. That is, since the entire molten prepolymer falls at a uniform speed as compared with the case where the molten prepolymer falls independently on each vertical wire 10, the residence time of the molten prepolymer is made more uniform in the polymerization vessel 100. This makes it possible to produce an aromatic polycarbonate having a uniform number average molecular weight with high productivity. Conventionally, the more the prepolymers that fall along the adjacent vertical wires 10 come into contact with each other, the smaller the surface area through which monohydroxy compounds (for example, phenol) by-produced in the polymerization reaction must be removed, the polymerization rate. Was thought to decline significantly. However, according to the study by the present inventors, the polymerization rate itself is not greatly reduced, and the amount of the melted prepolymer supplied to the wire guide 4 can be increased. The density of the molten prepolymer per unit cross-sectional area can be increased. As a result, the productivity can be greatly increased as compared with the case where the molten prepolymer is dropped in contact with each vertical wire 10 independently.

  Details such as the detailed structure of the wire guide 4 and the positional relationship between the polymer supply hole 12 and the wire guide 4 may be those described in Patent Document 1, which is incorporated herein by reference.

  Moreover, it is preferable to make the molten prepolymer absorb the inert gas from the inert gas supply port 9 before introducing it into the polymerization vessel 100 so that the surface area is increased by foaming during the polymerization. As a specific method for absorbing the inert gas into the molten prepolymer, the method described in International Publication No. 99/64492 can be used.

  The aromatic polycarbonate generated in the wire guide 4 falls from the lower end of the wire guide 4, but at least a part of the aromatic polycarbonate is formed on the tapered wall of the tapered lower portion (hereinafter also referred to as “casing bottom”) 13 c of the casing 13. Fall. The aromatic polycarbonate dropped on the tapered wall flows down toward the polymer discharge port 7 along the inner surface of the tapered wall along the inclination. The aromatic polycarbonate is extracted from the discharge pump 8 via the polymer discharge port 7. Usually, a predetermined amount of aromatic polycarbonate is retained in the tapered lower portion 13c. When the retention amount is small, it is difficult to discharge a certain amount of aromatic polycarbonate by the discharge pump 8, and when the retention amount of the aromatic polycarbonate is further reduced, the discharge pump 8 may cause cavitation. . The amount of the aromatic polycarbonate retained in the tapered lower portion 13c can be controlled by adjusting the discharge amount by the discharge pump 8 and a valve body (not shown) provided in the discharge path. At this time, the aromatic polycarbonate stays in the casing bottom 13c (hereinafter, the retained aromatic polycarbonate may be simply referred to as “retained matter”), and the liquid level contacts the tapered wall of the casing bottom 13c. To do.

In one aspect of this embodiment, the diameter (inner diameter) of the cylindrical upper portion (hereinafter also referred to as “casing trunk”) 13a in the casing 13 of the polymerization vessel 100 is 0.90 m or more and 10 m or less, and the casing In the virtual outermost peripheral portion where the aromatic polycarbonate flows down at the bottom 13c, the projected area S1 from the upper part in the vertical direction of the portion (X) where the aromatic polycarbonate flows down, and the upper portion in the vertical direction of the portion (Y) where the aromatic polycarbonate does not flow down. The projected area S2 satisfies the condition expressed by the following formula (1).
S1 / (S1 + S2)> 0.60 (1)

  The diameter of the casing body 13a is 0.90 m or more and 10 m or less. When the diameter is 0.90 m or more, the aromatic polycarbonate can be mass-produced with high productivity. Further, from the viewpoint of ease of manufacturing an actual polymerization vessel, the diameter of the casing body 13a is 10 m or less, and more preferably 8 m or less. The casing body 13a is cylindrical and preferably has the same diameter in any part in the height direction (vertical direction), but may have a different diameter in the height direction. When the casing body 13a has different diameters in the height direction, the minimum value is defined as the diameter of the casing body 13a. In addition, changes in the diameter due to the vacuum vent port 6 and the inert gas supply port 9 provided on the side wall of the casing body 13a are not considered in the calculation of the diameter of the casing body 13a. Furthermore, an observation window may be installed in the casing body 13a so that the casing bottom 13c can be observed.

  Moreover, the casing bottom 13c has a tapered shape that becomes thinner from the top to the bottom. Examples of the tapered shape include a cone shape (linear taper), an exponential taper, a parabolic taper, and a hemisphere. From the viewpoint of causing the aromatic polycarbonate to flow down more securely and making it difficult for the aromatic polycarbonate to adhere to the wall surface, it is preferable to have an inverted spindle shape that narrows from the top to the bottom, and from the top to the bottom. It is more preferable to have an inverted conical shape that becomes thinner.

  The “virtual outermost peripheral portion” refers to a region surrounded by a plurality of outermost points of the flowing-down portion (X) and straight lines connecting the plurality of outermost points. In addition, the “outermost point” is a projection (plan view) when the polymerization vessel 100 is viewed from above in the vertical direction, when a straight line is extended in an arbitrary direction from the center of the polymer discharge port 7. This means the point farthest from the intersection with the projection, but the point that does not have an outwardly convex shape that is surrounded by a straight line connecting the outermost points is excluded. These will be described in detail with reference to FIG. FIG. 2 is a schematic view showing an example of a polymerization apparatus used in the present embodiment, (A) is a schematic view of a polymerization vessel, and (B) is a schematic view showing a JJ cross section of the polymerization vessel. And (C) is an enlarged view showing the wire guide of (B), and (D) is a schematic view showing a part of the wire guide of (C). (A) is the same as FIG. 1 except that the stagnant and its liquid level L and JJ cross section are attached, and therefore the description thereof is omitted here. In (B), the plurality of wire guides 4a and 4b (hereinafter collectively referred to as “wire guide 4”) are configured by combining the vertical wire 10 and the fixing wire 11, respectively. In the center, a polymer outlet 7 is shown. And the outer edge in (C) which expanded (B) is an outer edge of a "virtual outermost peripheral part". That is, W is the most distant point among the intersections of the straight line geometrically extending from the center Z of the polymer discharge port 7 and the line indicating the projection of the wire guides 4a and 4b. A set of “outermost points” is a portion indicated by a thick line, and a straight line connecting those “outermost points” is a portion indicated by a thin line. Here, the point V is also the farthest point among the intersections between the straight line geometrically extended from the center Z of the polymer discharge port 7 and the line indicating the projection of the wire guides 4a and 4b. If the “outermost point” is included, the region does not have an outwardly convex shape, and the point V is excluded from the “outermost point”. Then, when the casing bottom portion 13c has an inverted conical shape that narrows from the top to the bottom, the hatched portion in (C) is defined as a portion (Y) that does not flow down in the virtual outermost peripheral portion.

  FIG. 3 is a schematic view showing a polymerization apparatus that is outside the scope of the present invention as will be described later. Like FIG. 2, (A) is a schematic view of the polymerization vessel, and (B) is the polymerization vessel. It is the schematic which shows the KK cross section of (C), (C) is an enlarged view which shows the wire guide of (B), (D) is the schematic which shows a part of wire guide of (C). In FIG. 3, two straight lines geometrically extended from the center Z of the polymer outlet 7 toward two adjacent outermost points W and a straight line connecting between the adjacent outermost points W The triangular portion surrounded by is defined as a portion (Y) where the polymer does not flow down. Here, as shown in FIG. 3, the discharge part located in the center is excluded from the part (Y) that does not flow down. Further, as shown in FIGS. 2 and 3, the straight line extending between adjacent “outermost points” W and the “outermost point” W are geometrically extended from the center Z of the polymer discharge port 7. Of the polygons surrounded by straight lines and lines indicating the projection of the wire guide, if there is no line indicating the projection of the wire guide inside the polygon (not including the surrounding area), the polymer flows down the polygon The portion (Y) not to be used. Here, the line indicating the projection of the wire guide means a straight line connecting the vertical wires at both ends of the wire guide when the wire guide is viewed from above.

In the present embodiment, it is desirable that the ratio of the portion (Y) that does not flow down is small in the virtual outermost peripheral portion. Specifically, the projected area S1 from the upper part in the vertical direction of the flowing part (X) in the virtual outermost peripheral part and the projected area S2 from the upper part in the vertical direction of the part (Y) not flowing down (FIG. 2C). The area of the hatched portion) satisfies the condition expressed by the following formula (1), more preferably satisfies the condition expressed by the following formula (1A), and more preferably expressed by the following formula (1B). The condition expressed by the following formula (1C) is satisfied, and still more preferably the condition expressed by the following formula (1D) is satisfied.
S1 / (S1 + S2)> 0.60 (1)
S1 / (S1 + S2)> 0.85 (1A)
S1 / (S1 + S2)> 0.95 (1B)
S1 / (S1 + S2)> 0.98 (1C)
S1 / (S1 + S2) ≧ 0.99 (1D)

  By setting the number, size, shape and arrangement of the wire guides 4 so as to satisfy this condition, the portion where the aromatic polycarbonate dropped from the wire guides 4 does not flow down compared to the case where the conditions are not satisfied (Y ) Can be reduced. As a result, even if the liquid level (indicated by symbol L in FIGS. 2A and 2C) of the accumulated matter in the casing bottom portion 13c rises and then falls, it remains in the portion (Y) that does not flow down. Less aromatic polycarbonate. As a result, even if the remaining aromatic polycarbonate deteriorates due to exposure to the surrounding atmosphere or thermal history, the liquid level L of the staying material rises again and is mixed into the staying product. It is possible to keep the amount of the group polycarbonates to a minimum. Further, the flow path of the polymer at the bottom of the polymerization vessel may change due to the difference in viscosity of the resin to be produced or the change in the state of the inner wall surface of the polymerization vessel. When the difference in viscosity of the resin is described in detail, when a resin product having a different viscosity is produced after producing a resin product having the same polymerizer viscosity, the flow path of the polymer at the bottom of the polymerizer May vary between resin products. In that case, when the latter resin product is produced, the flow path is changed, and a portion (residual portion) of the polymer is generated in the area that has become the flow path when the former resin product is produced. The part is exposed to the ambient atmosphere or is susceptible to thermal history. As a result, the remaining portion of the deteriorated polymer becomes a flow path for the polymer when the former resin product is produced again, and the deteriorated polymer is washed away. Even at this time, many deteriorated polymers are mixed into the product polymer. Even in such a case, the flow path of the polymer is difficult to change, and the region where the polymer flows is limited, so that the remaining part of the polymer is less likely to be generated, and the deteriorated polymer may be mixed into the stay. Can be suppressed. Degradation of an aromatic polycarbonate is that it becomes a high molecular weight by receiving a thermal history or being exposed to an ambient atmosphere, or gels depending on conditions. Such a deteriorated product can increase the molecular weight distribution of the aromatic polycarbonate product finally obtained or increase the branching amount, thereby deteriorating the physical properties, hue, and appearance of the product. However, as described above, in this embodiment, the amount of the deteriorated aromatic polycarbonate can be minimized. Therefore, the quality of the aromatic polycarbonate finally obtained can be maintained high.

  Further, in the casing bottom portion 13c, the relationship between the flow portion S1 and the non-flow portion S2 in the tapered wall region where the liquid level described later is 50% or less, particularly in the tapered wall region where it is 30% or less, is the above formula. The condition represented by (1) is preferably satisfied, the condition represented by the above formula (1A) is more preferably satisfied, the condition represented by the above formula (1B) is more preferably satisfied, and the above formula (1C) More preferably, the condition represented by the above formula (1D) is satisfied, and it is particularly preferable that S1 / (S1 + S2) does not become 1.00 (that is, S2 = 0). However, it is extremely preferable that S1 / (S1 + S2) is as close to 1.00 as possible. In such an area, depending on the height of the liquid level, frequent exposure to the surrounding atmosphere or contact with the accumulated matter is repeated, so that the advantages of the present invention can be enjoyed more effectively.

In another aspect of the present embodiment, in the circular portion formed by contact between the liquid level L of the aromatic polycarbonate staying in the casing bottom 13c and the inner surface of the tapered wall, the total length L0 of the circumference, Among them, the length L1 of the portion substantially in contact with the portion where the condensation polymerization reactive polymer flows down varies the liquid level L in a range satisfying the condition represented by the following formula (2). Furthermore, it is preferable to vary the liquid level L within a range that satisfies the condition represented by the following formula (2A).
L1 / L0> 0.90 (2)
L1 / L0 = 1.00 (2A)

  Here, the “circular portion” is a portion formed when the casing bottom portion 13c has an inverted conical shape that narrows from the top to the bottom, and is a circumference indicated by a dotted line in FIG. The part to be surrounded. When L1 / L0 exceeds 0.90, compared with the case where L1 / L0 is 0.90 or less, the contact with the portion where the aromatic polycarbonate does not flow down decreases. Thereby, even if it is a case where it falls when the liquid level L of a staying thing rises, the quantity of the aromatic polycarbonate which remains in the part which does not flow down decreases. Therefore, since the amount of the deteriorated aromatic polycarbonate mixed in the retained substance can be further minimized, the quality of the finally obtained aromatic polycarbonate product can be further maintained. In particular, when the condition represented by the above formula (2A) is satisfied, it means that the liquid level L is changed so as not to bring the retained matter into contact with the portion where the aromatic carbonate does not flow down. It becomes possible to maintain high quality.

  It is desirable to keep the position of the liquid level L as constant as possible. Specifically, the fluctuation level of the liquid level is maintained within 10%, preferably within 5%, and more preferably within 2%. Here, the “liquid level” means that the vertical position of the upper peripheral edge of the polymer outlet at the lower part of the polymerization vessel is 0%, and the upper peripheral edge of the casing bottom (that is, the lower peripheral edge of the casing body) The position of the liquid level in the vertical direction when the position in the vertical direction is 100% is shown as a percentage. In the polymerization vessel 100, the vertical position of the upper peripheral edge 7a of the polymer outlet 7 at the bottom of the polymerization vessel 100 is set to 0%, and the upper peripheral edge of the casing bottom 13c (that is, the lower peripheral edge 13e of the casing body 13a). The level of the liquid level in the vertical direction when the position in the vertical direction is 100% is the “liquid level”.

In the present embodiment, the residence time of the condensation polymerization reactive polymer that stays in the casing bottom 13c, for example, aromatic polycarbonate, is preferably within 3 hours, more preferably within 2 hours, and within 1 hour. Further preferred. By making this residence time within the above-mentioned range, it is possible to more effectively prevent the residence matter from receiving a thermal history at the casing bottom 13c, so that the resulting deterioration in the quality of the resin can be more effectively prevented. Is possible. Here, the “residence time” is defined as 0 when the time when it falls from the wire guide 4 and contacts the tapered wall of the casing bottom 13 c or when it falls directly on the stagnant is 0, and the discharge pump 8 located downstream of the polymer discharge port 7. The average time to pass is shown. “Residence time” is obtained by the following equation from the volume of the accumulated matter calculated from the liquid level at the casing bottom portion 13c and the amount of the accumulated matter extracted.
Residence time T (hours) = Volume of retained matter (L) / Amount of withdrawal of retained matter (L / hour)

  Also, the time from when the molten prepolymer passes through the raw material supply port 1 until the produced condensation polymerization reactive polymer passes through the discharge pump 8 (hereinafter referred to as “polymerizer passage time”) is within 5 hours. Preferably, it is within 3 hours, more preferably within 2 hours.

  In order to keep the residence time and the polymerization vessel passage time within the above-described ranges, the liquid level L of the residence may be kept as low as possible in the vertical direction. Specifically, if the liquid level is controlled to be preferably 50% or less, more preferably 30% or less, the residence time can be easily kept within the above range. Further, by increasing the length and capacity (diameter) of the pipe connecting the polymer discharge port 7 and the discharge pump 8, control may be performed so that the liquid level of accumulated matter exists in the pipe.

  In the polymerization apparatus of this embodiment, when producing an aromatic polycarbonate, the polymerization apparatus may include one polymerization apparatus 100 or two or more polymerization apparatuses 100, and may be used in combination. It is also possible to produce an aromatic polycarbonate by combining the polymerization vessel 100 according to this embodiment with another polymerization vessel. For example, a molten prepolymer is first produced by polymerizing an aromatic dihydroxy compound and diaryl carbonate using a stirred tank reactor, and the obtained molten prepolymer is used in the polymerizer 100 according to this embodiment. It is also preferred to polymerize using.

  As an apparatus for producing a melted prepolymer, in addition to the above-described stirred tank reactor, for example, a thin film reactor, a centrifugal thin film evaporation reactor, a surface renewal type biaxial kneading reactor, a biaxial horizontal type stirred reactor And wet wall reactors. In the present embodiment, by combining these, it is possible to proceed the condensation polymerization stepwise to produce the target molten prepolymer. For these production methods, reference can be made, for example, to US Pat. No. 5,589,564. In addition, the material of the polymerization reactor according to the present embodiment and other reactors is not particularly limited, and the material constituting at least the inner wall surface of the polymerization reactor or the reactor is a material selected from stainless steel, nickel, glass, and the like. It may be.

  In this embodiment, when manufacturing an aromatic polycarbonate by making an aromatic dihydroxy compound and diaryl carbonate react, reaction temperature is 50-350 degreeC normally, Preferably it is 100-290 degreeC. As this reaction proceeds, an aromatic monohydroxy compound is produced, and the reaction rate is increased by removing this from the reaction system. Accordingly, an inert gas such as nitrogen, argon, helium, carbon dioxide, or lower hydrocarbon gas that does not adversely affect the reaction is introduced into the polymerization reactor 100 or other reactors, and the aromatic monohydroxy compound produced is produced. A method of removing the gas accompanied with these gases and a method of performing the reaction under reduced pressure are also preferably used. What is necessary is just to introduce | transduce from the inert gas supply port 9, when introducing inert gas to the superposition | polymerization device 100. FIG.

  The preferred reaction temperature varies depending on the type, molecular weight, polymerization temperature, etc. of the aromatic polycarbonate to be produced. For example, in the case of producing an aromatic polycarbonate from bisphenol A and diphenyl carbonate, the number average molecular weight is less than 1000 and is in the range of 100 to 270. The range of ° C. is preferable, and the range of 200 to 290 ° C. is preferable in the range of 1000 or more.

  The preferred reaction pressure varies depending on the type and molecular weight of the aromatic polycarbonate to be produced, the polymerization temperature, and the like. For example, when producing an aromatic polycarbonate from bisphenol A and diphenyl carbonate, the number average molecular weight is less than 1000, and 50 mmHg ( The range of 6,660 Pa) to normal pressure is preferable, the number average molecular weight is in the range of 1000 to 2000, the range of 3 mmHg (400 Pa) to 50 mmHg (6,660 Pa) is preferable, and the number average molecular weight is over 2000, 20 mmHg (2,670 Pa) or less, particularly preferably 10 mmHg (1,330 Pa) or less, and more preferably 2 mmHg (267 Pa) or less. A method of carrying out the reaction under reduced pressure and introducing the aforementioned inert gas into the polymerization vessel 100 from the inert gas supply port 9 is also preferably used. It is also a preferred method to perform polymerization using a molten prepolymer in which an inert gas has been absorbed in advance.

  The polymerizer 100 according to this embodiment is suitably used as a main polymerizer for polymerizing polycarbonate using a polycarbonate prepolymer having a number average molecular weight of 2000 or more, more preferably 4000 or more as a raw material. There may be one main polymerization vessel or two or more main polymerization vessels. Further, the temperature in the main polymerization vessel is preferably 230 ° C. or higher and 300 ° C. or lower, and more preferably 240 ° C. or higher and 270 ° C. or lower. When this temperature is 230 ° C. or higher, it is possible to further suppress that a small part of the polymerization vessel or piping is in the temperature range of 180 ° C. to 220 ° C. due to insufficient heating or insufficient heat retention. This can further prevent clogging of a filter provided in the middle of a pipe or a polymer filter provided in an extruder due to crystallization of a prepolymer having a number average molecular weight of 1500 to 5000 in a short time. It becomes possible. Further, since the temperature in the main polymerization vessel is 270 ° C. or less, the aromatic polycarbonate is further prevented from becoming brittle due to an increase in the amount of branching in the aromatic polycarbonate when the residence time becomes long. Can do. However, when the temperature in the main polymerization vessel is increased, the polymerization rate is increased, the pressure during polymerization can be increased, and the production amount can be increased. In particular, in order not to increase the branching amount when the temperature is increased to 270 ° C. or higher, the residence time in the main polymerization vessel is preferably within 2 hours. The molecular weight of the desired polycarbonate product can be controlled by temperature, pressure in the polymerizer 100 and the amount of polycarbonate produced.

  By adjusting the temperature of the heating medium for heating the polymerization vessel 100 and / or the pressure in the polymerization vessel 100, the production amount of polycarbonate and the molecular weight of polycarbonate can be adjusted. For example, when it is desired to suppress the variation in the molecular weight of the polycarbonate with the same production amount, the molecular weight of the desired polycarbonate product can be controlled by adjusting the pressure in the polymerization vessel 100. It is also possible to control the molecular weight and production amount of the desired polycarbonate product by adjusting the temperature and pressure in the polymerization vessel 100. Furthermore, when using a plurality of polymerizers (of which at least one is the polymerizer 100), the temperature of the piping connecting the polymerizers can be controlled by the temperature of each polymerizer, and the viscosity and flow rate of the polycarbonate. It is also possible to control by adjusting. Further, the viscosity of the molten prepolymer at the raw material supply port 1 is lowered by using a separate heat medium system for the heating medium heating system of the raw material supply port 1 and the heating medium heating system of the main body of the polymerization apparatus 100 and / or a preheater. It becomes possible. The outlet pipe that discharges the polycarbonate from the polymerization vessel 100 may be branched into two to four. After branching, the polycarbonate may be supplied to an extruder or the like via the outlet pipe, and the additive may be mixed with the polycarbonate and pelletized. Alternatively, the polycarbonate may be supplied to a polymerizer further provided in the subsequent stage via the outlet pipe, and the polycarbonate may be further polymerized there. Furthermore, it is also preferable to add a catalyst, a branching agent, or the like to the polycarbonate from the middle of the outlet pipe for further polymerization. Further, for example, in order to adjust the amount of the terminal group of the polycarbonate, an aromatic diaryl compound or an aromatic dihydroxy compound is added to the polycarbonate discharged from the polymerization vessel 100 and further polymerized, and then the additive is mixed or added. It is also preferable to pelletize without mixing the agent.

  In the case where a plurality of polymerizers are provided (at least one of which is the polymerizer 100), by controlling the temperature of the piping connecting the polymerizers, it is possible to suppress the generation of foreign matters such as polycarbonate crystallized products and burnt polymers. Is possible. The difference (inlet-outlet) between the heat medium outlet temperature and the heat medium inlet temperature of the equipment and piping is preferably -20 ° C to 0.1 ° C, more preferably -15 ° C to 0.1 ° C,- More preferably, it is 10 to 0.1 ° C, and particularly preferably -5 to 0.1 ° C.

  From the viewpoint of preventing foreign matters from entering the polymerization vessel 100, a filter may be provided in the pipe connecting the outlet of the polymerization vessel installed upstream of the polymerization vessel 100 and the raw material supply port 1 of the polymerization vessel 100. preferable. The shape of the filter is not particularly limited, but a cone shape, a disk shape, and a cylindrical shape are preferable. The filter may be inserted into the pipe or may be a switching type such as a breaker plate used in an extruder.

  The aromatic polycarbonate obtained by the production method of the present embodiment is usually pelletized, but a molded product such as a film, a sheet, or a bottle may be produced by directly connecting the polymerization apparatus to a molding machine. Furthermore, in order to refine or remove the fish eye, a polymer filter or the like having a filtration accuracy of about 1 to 50 μm may be installed. Add / melt additives such as stabilizers, antioxidants, dyes / pigments, UV absorbers, flame retardants, and other additives such as glass fibers and fillers using an extruder or mixer. It can be kneaded and pelletized.

  According to this embodiment, a high-quality polycondensation reactive polymer having excellent molecular weight stability, for example, an aromatic polycarbonate, can be industrially produced with high productivity. Therefore, the molecular weight distribution is small, and the color tone has an appropriate branching amount. In addition, it is excellent in physical properties, and it is possible to reduce fish eyes caused by gel. In particular, even if the number average molecular weight of the aromatic polycarbonate is preferably 10,000 mol / g or more, more preferably 12000 mol / g or more, and even more preferably 13000 mol / g or more, the molecular weight distribution (Mw / Mn) is preferably 1. An aromatic polycarbonate of 0 to 3.0, more preferably 2.0 to 2.8, and even more preferably 2.0 to 2.6 can be obtained. Moreover, according to this embodiment, an aromatic polycarbonate excellent in physical properties and color tone having a branching amount of preferably 0.3 mol% or less, more preferably 0.27 mol% or less, and still more preferably 0.20 mol% or less is obtained. Can do.

  Although the present embodiment has been described in detail above, the present invention is not limited to the present embodiment. For example, the polymerization apparatus according to the present invention may be the polymerization apparatus shown in FIG. 4 instead of or in addition to the polymerization apparatus 100 described above. FIG. 4 is a schematic view showing another example of the polymerization apparatus used in the present invention. The polymerization vessel 200 in this polymerization apparatus is the same as the polymerization vessel 100 except for the shape of the tapered lower portion of the casing and the arrangement of the wire guide. In the superposition | polymerization device 200, arrangement | positioning of the wire guide 4 is as having shown to (B) which is the schematic which shows the MM cross section of the superposition | polymerization device 200. FIG. Even with such an arrangement of the wire guides 4, it is possible to satisfy the condition represented by the above formula (1) and to satisfy the condition represented by the above formula (2). The liquid level can be changed.

  Further, the shape of the tapered lower portion 213c of the casing 13 in the polymerization vessel 200 is as shown in (A), and the tapered lower portion 213c is further sandwiched between the tapered upper portion 213f and the tapered lower portion 213g. And a cylindrical middle portion 213h. In this case, it is preferable that the polycondensation reactive polymer flows down along the inner surface of the tapered wall of the tapered lower portion 213g. The tapered upper portion 213f and the tapered lower portion 213g have a tapered shape that becomes narrower from the top to the bottom, but the aromatic polycarbonate is more reliably allowed to flow down, and the aromatic polycarbonate is attached to the wall surface. From the viewpoint of making it difficult, it preferably has an inverted pyramid shape that narrows from above to below, and more preferably has an inverted cone shape that narrows from above to below.

  In addition, in the portion N connecting the tapered upper portion 213f and the cylindrical middle portion 213h, there is no portion where the condensation polymerization reactive polymer does not flow down, so that the region where the polymer does not flow down in the tapered lower portion 213c is efficient. It is preferable from the viewpoint of making it small. In this case, it is more preferable to control so that the liquid level L of the condensation polymerization reactive polymer (residue) staying in the tapered lower portion 213c exists in the cylindrical middle portion 213h. By doing so, in the cylindrical middle portion 213h, the condensation polymerization reactive polymer flows down, so that it remains on the wall surface above the liquid level L even when the liquid level L of the staying material is lowered after rising. It is possible to perform washing (self-cleaning) with the condensation polymerization reactive polymer flowing down the aromatic polycarbonate. In addition, the cylindrical middle portion 213h is less susceptible to aromatic polycarbonate remaining on the wall surface than the tapered portion, so even if the liquid level L rises and falls on the cylindrical middle portion 213h, the cylindrical wall portion 213h is aromatic on the wall surface. Easy to fall without polycarbonate attached.

  Furthermore, the guide may be a structure including at least a vertical wire, and is not limited to the wire guide 4.

  Furthermore, in the method for producing a polycondensation reactive polymer of the present invention, it is preferable to use a melted prepolymer with few foreign substances because a polymer with higher quality can be obtained. For production of the prepolymer, for example, a stirred tank type prepolymerizer (not shown) can be used. In addition, in order to promote the volatilization of by-products such as aromatic monohydroxy compounds during condensation polymerization in a wire type polymerizer, a wire type nitrogen absorption facility (not shown) is used for the purpose of preliminarily absorbing nitrogen. Can also be used. Furthermore, a wire-type final polymerizer (not shown) may be used to produce a higher molecular weight polymer from the polymer produced in the main polymerizer. Here, the “wire type” means a system in which a predetermined process is performed while dropping a molten or liquid raw material or supply material along a guide such as a wire with its own weight.

From the viewpoint of removing foreign substances in the prepolymer and the polymer, in the method for producing the condensation polymerization reactive polymer of the present invention, the transfer of the prepolymer connected from the bottom of the stirred tank type prepolymerizer to the apparatus used in the subsequent process At least one of the prepolymer and / or polymer supply port or discharge port in the discharge pipe where the pump is installed, the wire type nitrogen absorption facility, the main polymerization device, and the wire type final polymerization device, a filter (see FIG. (Not shown) is preferably installed. Examples of the type of filter include a cone type filter, a disk type filter, and a breaker plate type filter (all not shown) provided at the discharge of the extruder, and these are preferable.
The hole diameter of a cone type filter element is usually slightly smaller than the hole diameter of a polymer dispersion plate provided in a wire-type polymerization vessel, a nitrogen absorption facility, or the like. Specifically, the pore size of the filter is preferably 0.05 to 3 mm smaller than the pore size of the polymer dispersion plate. The pore diameter is preferably 0.1 to 2 mm smaller, and more preferably 0.1 to 1 mm smaller.
When using a discharge pipe that is directly connected to the transfer pump and provided with a filter, the discharge pipe is divided into an L-shaped (elbow) with a discharge pressure gauge (not shown) attached to facilitate replacement of the filter element. It is preferable to use pipe piping. In order to replace the filter, it is also preferable that the discharge pipe can be washed with a raw material (for example, an aromatic monohydroxy compound).
Moreover, when the heat medium oil supplied from the heat medium boiler of the heating source is used, and the pipe through which the heat medium oil flows has an L-shaped double pipe part, the L-shaped double pipe part is It is also preferable that the heat medium oil has a shape and structure that allows the heat medium oil to be drained by providing a bypass pipe and partially stopping the flow of the heat medium oil. The discharge pressure gauge is preferably provided upstream of the filter in order to grasp the operation state of the transfer pump, the number average molecular weight of the prepolymer and / or polymer, the viscosity change, and the clogging state of the filter. Furthermore, it is preferable to use an inverted L-shaped elbow pipe part of a pipe for supplying a prepolymer to a main polymerizer such as a wire type. By using the elbow piping part, the filter (filter element) can be replaced and inspected more efficiently.

Hereinafter, the contents of the present invention will be described more specifically with reference to examples and comparative examples.
Evaluation of each item was measured by the following method.

(1) Number average molecular weight and molecular weight distribution Gel permeation chromatography (manufactured by Tosoh Corporation, product name “HLC-8320GPC”, column: Tosoh Corporation, product name “TSK-GEL Super Multipore HZ-M” , RI detector), and tetrahydrofuran was used as an eluent, and measurement was performed at a temperature of 40 ° C. The molecular weight (number average molecular weight and weight average molecular weight) was determined from a calibration curve of standard monodisperse polystyrene (manufactured by VARIAN, product name “EasiVial”) using a converted molecular weight calibration curve according to the following equation.
M _PC = 0.3591 × M _PS ^1.0388
Here, in the formula, _MPC is the number average molecular weight or weight average molecular weight of the polymer, and MPS is the number average molecular weight or weight average molecular weight of the standard monodisperse polystyrene.

(2) Fisheye From the obtained polymer, a film molding machine (manufactured by Tanabe Plastic Machinery Co., Ltd., 30 mmφ single screw extruder, screw rotation speed: 100 rpm, discharge amount: 10 kg / hr, barrel temperature: 280 ° C., T die temperature: A film having a thickness of 50 μm and a width of 30 cm was formed using a temperature of 260 ° C. and a roll temperature of 120 ° C., and the number of fish eyes having a size of 300 μm or more in an arbitrary length of 1 m was visually counted.

(3) Viscosity The viscosities of the raw material prepolymer and the obtained polymer were measured at respective temperatures corresponding to Examples and Comparative Examples by sampling each sample. As a measuring device, a capillograph manufactured by Toyo Seiki (product name “CAPIROGRAPH 1B”, model number A-271902103) was used.
The amount of branching was indicated by the total amount of the heterogeneous binding units (A) and heterogeneous binding units (B) described in WO 97/32916, and was determined according to the method described in WO 97/32916.

Example 1
Aromatic polycarbonate was produced using the guide contact flow type polymerizer of FIG. 1 having the arrangement of the wire guide 4 as shown in FIG. As for the shape of the casing 13, the casing upper part 13a was cylindrical, and the casing bottom 13c was an inverted cone. In the guide contact drop polymerization reaction zone 5 shown in FIG. 2A, the casing body 13a has a cylindrical shape with an inner diameter of 1500 mm and a length of 10,000 mm. As shown in FIG. 2D, twelve wire guides 4 provided with fixing wires 11 on one side of the plurality of vertical wires 10 were installed as shown in FIG.

  Here, 102 pieces of the vertical wires 10 in the wire guide 4a were arranged at intervals of 10 mm in the manner shown in FIG. The diameter of the vertical wire 10 was 3 mm, and the length in the horizontal direction from one end to the other end of the wire guide 4a was 1010 mm. Therefore, the total number of the vertical wires 10 in the six wire guides 4a was 612.

  A plurality of polymer supply holes 12 through which the molten prepolymer flows down were installed on the upper part of the vertical wire 10. The polymer supply holes 12 were installed directly above the vertical wires 10 so that the distance between the centers of the polymer supply holes 12 was 30 mm. The installation interval and the number of installation of the polymer supply holes 12 were 34 in total from every second vertical wire from the second upper part from the end of the vertical wire 10.

  Moreover, 54 pieces of the vertical wires 10 in the wire guide 4b were arranged at intervals of 10 mm in an embodiment as shown in FIG. The diameter of the vertical wire 10 was 3 mm, and the length in the horizontal direction from one end to the other end of the wire guide 4b was 530 mm. Therefore, the total number of the vertical wires 10 in the six wire guides 4b was 324.

  A plurality of polymer supply holes 12 through which the molten prepolymer flows down were installed on the upper part of the vertical wire 10. The polymer supply holes 12 were installed directly above the vertical wires 10 so that the distance between the centers of the polymer supply holes 12 was 30 mm. The installation interval and the number of installation of the polymer supply holes 12 were installed every two vertical wires from the second upper part from the end of the vertical wire 10.

  The interval (pitch) between the plurality of fixing wires 11 extending in the horizontal direction was 80 mm. Table 1 shows other wire guide sizes and the like. Moreover, all the materials of the polymerization vessel were SUS316, the outside of the polymerization vessel was a jacket, and it was heated to 260 ° C. with a heat medium.

  A molten prepolymer (a precursor of an aromatic polycarbonate; number average molecular weight (Mn) of 4500) produced from bisphenol A and diphenyl carbonate (1.08 molar ratio of bisphenol A to 1.08) and maintained at 260 ° C. The material was continuously supplied from the material supply port 1 to the material supply zone 3 by a supply pump. The molten prepolymer continuously supplied to the guide contact drop polymerization reaction zone 5 from the plurality of polymer supply holes 12 formed in the distribution plate 2 in the polymerization vessel 100 flows down along the wire guide 4, and accordingly. The polymerization reaction proceeded. The molten prepolymer discharged from the polymer supply hole 12 falls along the wire guide 4 installed below the polymer supply hole 12 and contacts each other in the horizontal direction below 200 mm from the upper end of the wire guide 4. Thereby, the falling molten prepolymer / aromatic polycarbonate mass had a “planar” appearance. The obtained aromatic polycarbonate dropped on the inner surface of the tapered wall of the casing bottom 13c.

  The aromatic polycarbonate dropped on the inner surface of the tapered wall flowed down toward the inverted conical apex of the casing bottom 13c by gravity, and dropped into the pipe from the polymer discharge port 7 provided there. In FIG. 2C, the hatched portion is a projection of a portion (Y) where the aromatic polycarbonate does not flow down, and a portion (Y) where the aromatic polycarbonate does not flow down geometrically is a projection view from above in the vertical direction. It is shown. Moreover, the outermost frame in (C) of FIG. 2 is a frame of the virtual outermost peripheral portion, and the portion other than the portion (Y) that does not flow down of the virtual outermost peripheral portion is a portion where the aromatic polycarbonate flows down ( X).

  The relationship between the projected area S1 and the projected area S2 was S1 / (S1 + S2) = 0.94.

  The aromatic polycarbonate that has dropped from the lower end of the wire guide 4 onto the tapered wall of the casing bottom 13c of the polymerization vessel 100 is continuously connected from the polymer outlet 7 by the discharge pump 8 so that the amount staying at the casing bottom 13c is substantially constant. Extracted.

  As shown in FIGS. 2A and 2C, the liquid level of the staying material is located at the casing bottom 13c, and the liquid level of the staying material varies within a range of 10% ± 2%. Thus, the output of the discharge pump 8 was controlled.

  At this time, since the liquid level was controlled so that the liquid surface exists only in the portion (X) where the aromatic polycarbonate flows down, the liquid surface and the tapered wall of the aromatic polycarbonate staying in the tapered lower portion. The ratio L1 / L0 between the total length L0 of the circumference of the circular part formed in contact with the inner surface of the glass and the length L1 of the part in contact with the part where the aromatic polycarbonate flows down is 1.00. there were.

  The degree of vacuum in the guide contact drop polymerization reaction zone 5 was adjusted so that the number average molecular weight of the aromatic polycarbonate extracted from the polymer outlet 7 through the vacuum vent 6 was 12800. The number average molecular weight of the aromatic polycarbonate obtained every hour was measured. After confirming that the number average molecular weight was 12800 ± 100 continuously for 10 hours, the supply amount of the molten prepolymer and the extraction amount of the aromatic polycarbonate were increased stepwise. As a result, aromatic polycarbonate having a number average molecular weight of 12800 ± 100 could be stably produced until the amount of aromatic polycarbonate extracted (stable production rate) reached 6 kg / (hr · 100 mm). The extraction amount here means the production amount per 100 mm in the horizontal direction in the wire guide 4 composed of a plurality of vertical wires 10, and the unit is a value expressed in kg / (hr · 100 mm). Moreover, the weight average molecular weight of the obtained aromatic polycarbonate was 36000, and molecular weight distribution was 2.8. The residence time of the staying thing in the casing bottom part 13c was 50 minutes. Further, the branching amount was 0.26 mol%, and the number of fish eyes was 0. The above results are summarized in Table 1. In Table 1, the viscosity value of the molten prepolymer is a value measured at 260 ° C. In addition, fish eyes of 50 μm or more that can be visually observed were not observed. Moreover, the production amount of the aromatic polycarbonate was 600 kg / h, and the mass production was possible with high productivity.

(Examples 2 to 13)
As shown in Table 1, an aromatic polycarbonate was obtained in the same manner as in Example 1 except that various conditions were changed. Various physical properties and evaluation results of the obtained aromatic polycarbonate are summarized in Table 1. In Examples 3 and 4, the arrangement of the wire guide is changed from the one shown in FIG. 4B to the one shown in FIG. 5A. The arrangement was changed from the one shown in FIG. 4B to the one shown in FIG. 5B. Moreover, in Example 4, the wire guide which is not provided with the fixed wire was used. Moreover, L1 / L0 in Examples 2 to 10 and 13 was 1.00.
Further, in Example 11, in addition to the changes shown in Table 1, the distance between wire guides 400 mm was changed to 280 mm (thus 480 mm was changed to 540 mm), and 720 mm was changed to 240 mm (thus 320 mm was changed to 560 mm). Except for this, the same polymerization vessel as in FIG. 3 described in detail below was used. In addition, L1 / L0 of Example 11 was 0.78.
Furthermore, in Example 12, in addition to the changes shown in Table 1, the distance between wire guides 400 mm was changed to 160 mm (thus 480 mm was changed to 600 mm), and 720 mm was changed to 240 mm (thus 320 mm was changed to 560 mm). Except for this, the same polymerization vessel as in FIG. 3 described in detail below was used. In addition, L1 / L0 of Example 12 was 0.81.

(Comparative Example 1)
Polycarbonate was produced using a polymerizer in which the inner diameter of the casing body 13a was 300 mm and 21 vertical wires were arranged in a row. Other conditions were the same as in Example 1. The liquid level (L) was kept constant for 30 minutes to produce a polycarbonate having a number average molecular weight (Mn) of 10300. The obtained polymer had two fish eyes, which were relatively good, but the production was extremely low at 32 kg / h.

(Comparative Example 2)
An attempt was made to uniformly arrange 400 vertical wires using a polymerization vessel having an inner diameter of the casing body 13a of 2000 mm, but it was difficult to design due to difficulties in manufacturability and load resistance.

(Comparative Example 3)
Aromatic polycarbonate was produced using the guide contact flow type polymerizer of FIG. 1 having the arrangement of the wire guide 4 as shown in FIG. Except for the arrangement of the wire guide 4, for example, the shape of the casing 13 was the same as that in Example 1. The guide contact drop polymerization reaction zone 5 shown in FIG. 3A has a cylindrical shape with an inner diameter of the casing body 13a of 2000 mm and a length of 10,000 mm. FIG. 4B is a schematic view of the wire guide 4 provided with the fixing wire 11 on one side of the plurality of vertical wires 10 as shown in FIG. As shown in FIG. Note that (A) to (D) in FIG. 3 correspond to (A) to (D) in FIG.

  Here, nine vertical wires 10 in one wire guide 4 are arranged at intervals of 60 mm in the manner shown in FIG. 3D, and the diameter of the vertical wires 10 is 3 mm. The length in the horizontal direction from one end to the other was 480 mm. Therefore, the total number of the vertical wires 10 in the 20 wire guides 4 was 180.

  A plurality of polymer supply holes 12 through which the molten prepolymer flows down were installed on the upper part of the vertical wire 10. The polymer supply hole 12 was installed right above all the vertical wires.

  The interval (pitch) between the plurality of fixing wires 11 extending in the horizontal direction was 80 mm. Table 1 shows other wire guide sizes and the like. Further, the material of the polymerization vessel was all SUS316, and the outside of the polymerization vessel was a jacket, which was heated to 265 ° C. with a heat medium.

  A molten prepolymer (precursor of aromatic polycarbonate; number average molecular weight (Mn) is 4500) prepared from bisphenol A and diphenyl carbonate (1.08 molar ratio of bisphenol A) and kept at 265 ° C. The material was continuously supplied from the material supply port 1 to the material supply zone 3 by a supply pump. The molten prepolymer continuously supplied from the plurality of polymer supply holes 12 formed in the distribution plate 2 in the polymerization vessel 100 to the guide contact drop polymerization reaction zone 5 flows down along the wire guide 4 and is polymerized accordingly. The reaction proceeded. The molten prepolymer discharged from the polymer supply hole 12 falls along the wire guide 4 installed below the polymer supply hole 12, and flows down downward from the upper end of the wire guide 4, while being aromatic. It was converted into polycarbonate and dropped independently onto the inner surface of the tapered wall of the casing bottom 13c.

  The aromatic polycarbonate dropped on the inner surface of the tapered wall flowed down toward the inverted conical apex of the casing bottom 13c by gravity, and dropped into the pipe from the polymer discharge port 7 provided there. In FIG. 3C, the hatched portion is a projection of a portion (Y) where the aromatic polycarbonate does not flow down, and a geometrical portion (Y) where the aromatic polycarbonate does not flow down is a projection view from above in the vertical direction. It is shown. Since the aromatic polycarbonate falls independently from the vertical wire 10, there are a large number of portions (Y) that do not flow down even in the portions that are not shown by hatching in FIG.

  The outermost frame in (C) of FIG. 3 is the frame of the virtual outermost peripheral portion, and the portion (X) where the aromatic polycarbonate flows down to the portion other than the portion (Y) that does not flow down of the virtual outermost peripheral portion. ) Was recognized.

  The relationship between the projected area S1 and the projected area S2 was S1 / (S1 + S2) <0.5. L1 / L0 was 0.53.

  The aromatic polycarbonate that has dropped from the lower end of the wire guide 4 onto the tapered wall of the casing bottom 13c of the polymerization vessel 100 is continuously connected from the polymer outlet 7 by the discharge pump 8 so that the amount staying at the casing bottom 13c is substantially constant. Extracted.

  As shown in FIGS. 3A and 3C, the liquid level of the staying material is located at the casing bottom 13c, and the liquid level of the staying material varies within a range of 30% ± 20%. Thus, the output of the discharge pump 8 was controlled.

  At this time, since the liquid level was controlled so that the liquid level was present even in the portion (Y) where the aromatic polycarbonate did not flow down, the aromatic adhering to the portion (Y) that did not flow down due to the rise in the liquid level. The polycarbonate remained in the portion (Y) where it did not flow down due to the lowering of the liquid level, and received a heat history. As a result, the aromatic polycarbonate which received the heat history was mixed into the staying material when the liquid level rose again and discharged from the polymer outlet 7.

  The degree of vacuum in the guide contact drop polymerization reaction zone 5 was adjusted so that the number average molecular weight of the aromatic polycarbonate extracted from the polymer outlet 7 through the vacuum vent 6 was 12800. The number average molecular weight of the aromatic polycarbonate obtained every hour was measured. After confirming that the number average molecular weight was 12800 ± 100 continuously for 10 hours, the supply amount of the molten prepolymer and the extraction amount of the aromatic polycarbonate were increased stepwise. As a result, aromatic polycarbonate having a number average molecular weight of 12800 ± 100 could be stably produced until the amount of aromatic polycarbonate extracted (stable production rate) reached 1.5 kg / (hr · 100 mm). The extraction amount here means the production amount per 100 mm in the horizontal direction in the wire guide 4 composed of a plurality of vertical wires 10, and the unit is a value expressed in kg / (hr · 100 mm). Moreover, the weight average molecular weight of the obtained aromatic polycarbonate was 45000, and molecular weight distribution was 3.5. The residence time of the staying thing in the casing bottom part 13c was 4 hours. There were 10 fish eyes. The results are shown in Table 1.

(Comparative Example 4)
An aromatic polycarbonate was produced in the same manner as in Comparative Example 3, except that the interval between the vertical wires 10 was 10 mm (980 vertical wires 10 in total). The relationship between the projected area S1 and the projected area S2 was S1 / (S1 + S2) <0.5, and L1 / L0 was 0.55. The number of fish eyes was eight.

  This application is based on a Japanese patent application filed on March 19, 2014 (Japanese Patent Application No. 2014-057195), the contents of which are incorporated herein by reference.

  According to the present invention, a high-quality polycondensation reactive polymer having excellent molecular weight stability, particularly an aromatic polycarbonate, can be produced industrially with high productivity, so that the molecular weight distribution is small, the amount of branching is appropriate, and the color and physical properties. In addition, it is possible to reduce fish eyes caused by gel. Therefore, there is industrial applicability when producing polycondensation reactive polymers such as aromatic polycarbonates.

  DESCRIPTION OF SYMBOLS 1 ... Raw material supply port, 2 ... Distribution plate, 3 ... Raw material supply zone, 4 ... Wire guide, 5 ... Guide contact fall polymerization reaction zone, 6 ... Vacuum vent port, 7 ... Polymer discharge port, 8 ... Discharge pump, 9 ... Inert gas supply port, 10 ... vertical wire (vertical wire), 11 ... horizontal wire (fixing wire), 12 ... polymer supply hole, 13 ... casing, 100, 200 ... guide contact drop polymerizer (polymerization) vessel).

Claims (14)

The following steps (I) and (II):
(I) A polymerization vessel for producing a polycondensation reactive polymer, comprising a casing, a guide provided in the casing, and a polymer outlet connected to the casing and provided below the casing. Supplying molten prepolymer to the vessel; and
(II) a step of allowing the molten prepolymer to flow down while contacting the surface of the guide to polymerize the molten prepolymer, thereby producing the condensation polymerization reactive polymer;
A method for producing a condensation-polymerization reactive polymer having
The casing includes a cylindrical upper portion having a lower end peripheral portion having a diameter larger than a diameter of the upper end peripheral portion of the polymer outlet, the lower end peripheral portion of the cylindrical upper portion, and the upper end peripheral portion of the polymer outlet. And a tapered lower portion having a tapered wall extending from the lower edge periphery to the upper edge periphery, and the casing, the guide, and the polymer outlet are dropped from the guide The polycondensation reactive polymer is arranged to flow down to the polymer outlet along the inner surface of the tapered wall while staying in the tapered lower part,
The diameter of the cylindrical upper part is 0.90 m or more and 10 m or less,
In a virtual outermost peripheral portion where the condensation polymerization reactive polymer flows down in the tapered lower part, a projected area S1 from above in a vertical direction of the portion where the condensation polymerization reactive polymer flows down, and the condensation polymerization reactive polymer includes A manufacturing method in which a projected area S2 from above in a vertical direction of a portion that does not flow down satisfies a condition represented by the following formula (1).
S1 / (S1 + S2)> 0.60 (1) The manufacturing method according to claim 1, wherein the projected area S1 and the projected area S2 satisfy a condition represented by the following formula (1A).
S1 / (S1 + S2)> 0.85 (1A) The manufacturing method according to claim 1, wherein the projected area S1 and the projected area S2 satisfy a condition represented by the following formula (1B).
S1 / (S1 + S2)> 0.95 (1B)   The said guide is a wire guide provided with a some vertical wire, Comprising: The stable production rate of the said polycondensation reactive polymer is 5 kg / (hr * 100mm) or more, The any one of Claims 1-3. Manufacturing method. The following steps (I) and (II):
(I) A polymerization vessel for producing a polycondensation reactive polymer, comprising a casing, a guide provided in the casing, and a polymer outlet connected to the casing and provided below the casing. Supplying molten prepolymer to the vessel; and
(II) a step of allowing the molten prepolymer to flow down while contacting the surface of the guide to polymerize the molten prepolymer, thereby producing the condensation polymerization reactive polymer;
A method for producing a condensation-polymerization reactive polymer having
The casing includes a cylindrical upper portion having a lower end peripheral portion having a diameter larger than a diameter of the upper end peripheral portion of the polymer outlet, the lower end peripheral portion of the cylindrical upper portion, and the upper end peripheral portion of the polymer outlet. And a tapered lower portion having a tapered wall extending from the lower edge periphery to the upper edge periphery, and the casing, the guide, and the polymer outlet are dropped from the guide The polycondensation reactive polymer is disposed so as to flow down to the polymer outlet along the inner surface of the tapered wall while staying in the tapered lower part,
In a circular portion formed by contacting the liquid surface of the condensation polymerization reactive polymer staying in the tapered lower portion and the inner surface of the tapered wall, the total length L0 of the circumference, and the condensation polymerization of the circumference The manufacturing method of changing the said liquid level in the range which the length L1 of the part which contacts the part which a reactive polymer flows down substantially satisfies the conditions represented by following formula (2).
L1 / L0> 0.90 (2) The manufacturing method according to claim 5, wherein the liquid level is varied within a range in which the total length L0 and the length L1 satisfy a condition represented by the following formula (2A).
L1 / L0 = 1.00 (2A) The tapered lower portion further has a tapered upper portion, a tapered lower portion, and a cylindrical middle portion sandwiched between them,
In the portion connecting the tapered upper portion and the cylindrical middle portion, there is no portion where the condensation polymerization reactive polymer does not flow down, and the liquid level of the condensation polymerization reactive polymer staying in the tapered lower portion Is controlled so as to be present in the cylindrical middle part.   The manufacturing method of any one of Claims 1-7 whose residence time of the said polycondensation reactive polymer which stays in the said taper-shaped lower part is less than 3 hours.   The guide is a wire guide, and the polycondensation reactive polymer drops the wire guide while forming a planar fluid by contacting and integrating the different wire guides. The manufacturing method of the polycondensation reactive polymer of any one of 1-8.   The manufacturing method of any one of Claims 1-9 whose said polycondensation reactive polymer is an aromatic polycarbonate. An apparatus for producing a polycondensation reactive polymer comprising a polymerization vessel for producing the polycondensation reactive polymer,
The polymerizer is a casing, a guide provided in the casing, and a guide for polymerizing the molten prepolymer by bringing the molten prepolymer into contact with the surface of the casing, and connected to the casing. With a polymer outlet provided below,
The casing includes a cylindrical upper portion having a lower end peripheral portion having a diameter larger than a diameter of the upper end peripheral portion of the polymer outlet, the lower end peripheral portion of the cylindrical upper portion, and the upper end peripheral portion of the polymer outlet. And a tapered lower portion having a tapered wall extending from the lower edge periphery to the upper edge periphery, and the casing, the guide, and the polymer outlet are dropped from the guide The polycondensation reactive polymer is arranged to flow down to the polymer outlet along the inner surface of the tapered wall while staying in the tapered lower part,
In a virtual outermost peripheral portion where the condensation polymerization reactive polymer flows down in the tapered lower part, a projected area S1 from above in a vertical direction of the portion where the condensation polymerization reactive polymer flows down, and the condensation polymerization reactive polymer includes The manufacturing apparatus in which the projected area S2 from above in the vertical direction of the portion that does not flow down satisfies the condition represented by the following formula (1).
S1 / (S1 + S2)> 0.60 (1)   The manufacturing apparatus according to claim 11, wherein the tapered lower portion further includes a tapered upper portion, a tapered lower portion, and a cylindrical middle portion sandwiched therebetween.   In the portion connecting the tapered upper portion and the cylindrical middle portion, there is no portion where the condensation polymerization reactive polymer does not flow down, and the liquid level of the condensation polymerization reactive polymer staying in the tapered lower portion The manufacturing apparatus according to claim 12, which can be controlled to exist in the cylindrical middle part.   The manufacturing apparatus according to any one of claims 11 to 13, wherein the polycondensation reactive polymer is an aromatic polycarbonate.

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