WO2015141501A1 - 縮重合反応性ポリマー及びその製造装置 - Google Patents

縮重合反応性ポリマー及びその製造装置 Download PDF

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WO2015141501A1
WO2015141501A1 PCT/JP2015/056746 JP2015056746W WO2015141501A1 WO 2015141501 A1 WO2015141501 A1 WO 2015141501A1 JP 2015056746 W JP2015056746 W JP 2015056746W WO 2015141501 A1 WO2015141501 A1 WO 2015141501A1
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Prior art keywords
polymer
reactive polymer
casing
tapered
guide
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PCT/JP2015/056746
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English (en)
French (fr)
Japanese (ja)
Inventor
宗明 網中
和美 長谷川
安田　和治
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旭化成ケミカルズ株式会社
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Priority to EA201691665A priority Critical patent/EA032233B1/ru
Priority to JP2016508661A priority patent/JP6230695B2/ja
Priority to CN201580003488.6A priority patent/CN105873980B/zh
Priority to KR1020167014868A priority patent/KR101861938B1/ko
Publication of WO2015141501A1 publication Critical patent/WO2015141501A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/247—Suited for forming thin films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/205—General preparatory processes characterised by the apparatus used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00768—Baffles attached to the reactor wall vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/192—Details relating to the geometry of the reactor polygonal
    • B01J2219/1923—Details relating to the geometry of the reactor polygonal square or square-derived
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1946—Details relating to the geometry of the reactor round circular or disk-shaped conical

Definitions

  • 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 of great demand among engineer plastics.
  • Typical examples include polycarbonate, polyamide, and polyester resins such as PET bottles.
  • 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.
  • 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.
  • 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.
  • 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.
  • the remaining polymer 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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).
  • 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.
  • 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.
  • 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 1.00
  • 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 [6]
  • 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.
  • 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.
  • 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
  • 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).
  • the present embodiment 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.
  • 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.
  • the same elements are denoted by the same reference numerals, and redundant description is omitted.
  • the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified.
  • the dimensional ratios in the drawings are not limited to the illustrated ratios.
  • “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.
  • 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.
  • 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)
  • the method for producing a condensation polymerization reactive polymer 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 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.
  • 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.
  • the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and the like.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT polytrimethylene terephthalate
  • a typical example of the polycarbonate resin is an aromatic polycarbonate obtained by reacting an aromatic hydroxy compound with diaryl carbonate.
  • a representative example of the polycarbonate resin in the present embodiment includes an aromatic polycarbonate obtained by reacting an aromatic hydroxy compound with diaryl carbonate.
  • aromatic dihydroxy compound one kind may be used alone, or two or more kinds may be used in combination.
  • a typical example of the aromatic dihydroxy compound is bisphenol A.
  • 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.
  • 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, etc., and is not particularly limited.
  • the diaryl carbonate is preferably 0.9 to 2.5 moles, more preferably 0.95 to 2.0 moles, and still more preferably 0.98 to 1.5 moles per mole of the aromatic dihydroxy compound. Used.
  • an aromatic monohydroxy compound such as phenol, t-butylphenol, cumylphenol or the like may be used in combination for terminal conversion and molecular weight adjustment.
  • a polyfunctional compound may be used in combination in order to introduce a branched structure into the condensation polymerization reactive polymer as long as the object of the present invention is not impaired.
  • 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.
  • 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 usually 1.0 ⁇ 10 ⁇ 8 to 1.0 part by mass with respect to 100 parts by mass of the raw material aromatic dihydroxy compound.
  • it is selected in the range of 1.0 ⁇ 10 ⁇ 7 to 1.0 ⁇ 10 ⁇ 1 parts by mass.
  • the number average molecular weight is preferably in the range of 500 to 100,000, more preferably in the range of 2,000 to 30,000.
  • the number average molecular weight can be measured using gel permeation chromatography (GPC).
  • molten prepolymer means a melt during polymerization.
  • 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.
  • 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 view showing 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.
  • wire guide for producing a polycondensation reactive polymer
  • 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.
  • 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
  • polymerizer 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 more detail with reference to FIG.
  • polymerizer a guide contact drop polymerizer
  • the condensation polymerization reactive polymer is an aromatic polycarbonate
  • the present invention is not limited to those described below.
  • the molten prepolymer is supplied to the polymerization vessel 100 from the raw material supply port 1.
  • 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.
  • molten prepolymer or the like 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.
  • the wire guide 4 falls while exhibiting a “planar” appearance.
  • 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.
  • a polymerization vessel in which vertical wires are arranged so as to form this planar fluid.
  • 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.
  • 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.
  • 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 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.
  • Mn number average molecular weight
  • 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.
  • 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.
  • the molten prepolymer absorbs the inert gas from the inert gas supply port 9 before being introduced into the polymerization vessel 100 so that the surface area is increased by foaming during the polymerization.
  • 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.
  • 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.
  • 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).
  • 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.
  • the casing bottom 13c has a tapered shape that becomes thinner from the upper side to the lower side.
  • the tapered shape include a cone shape (linear taper), an exponential taper, a parabolic taper, and a hemisphere.
  • 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 above “virtual outermost peripheral portion” refers to a region surrounded by a plurality of outermost points of the flowing down portion (X) and a straight line connecting the plurality of outermost points.
  • 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.
  • 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
  • (B) is a schematic view showing a JJ cross section of the polymerization vessel.
  • (C) is an enlarged view showing the wire guide of (B)
  • (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 the description thereof is omitted here.
  • 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.
  • a polymer outlet 7 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.
  • 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.
  • 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.
  • (A) is a schematic view of the polymerization vessel
  • (B) is the polymerization vessel.
  • FIG. 2 is a schematic view showing a cross-section of KK
  • (C) is an enlarged view showing a wire guide of (B)
  • (D) is a schematic view showing a part of the wire guide of (C).
  • the triangular portion surrounded by is defined as a portion (Y) where the polymer does not flow down.
  • Y portion where the polymer does not flow down.
  • the discharge part located in the center is excluded from the part (Y) that does not flow down.
  • 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.
  • 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.
  • the ratio of the portion (Y) that does not flow down is small in the virtual outermost peripheral portion.
  • 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.
  • 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.
  • 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.
  • the liquid level L of the staying material rises again and is mixed into the staying product.
  • 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.
  • 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.
  • 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 “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.
  • 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.
  • the quality of the finally obtained aromatic polycarbonate product can be further maintained.
  • the condition represented by the above formula (2A) 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.
  • the position of the liquid level L is kept constant as possible. Specifically, the fluctuation level of the liquid level is maintained within 10%, preferably within 5%, and more preferably within 2%.
  • 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.
  • 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”.
  • the residence time of the condensation polymerization reactive polymer that stays in the casing bottom 13c 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.
  • 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.
  • 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)
  • 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.
  • 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.
  • the polymerization apparatus when producing an aromatic polycarbonate, may include one polymerization vessel 100 or two or more, 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.
  • 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.
  • the reaction temperature is usually 50 to 350 ° C., preferably 100 to 290 ° C.
  • an aromatic monohydroxy compound is produced, and the reaction rate is increased by removing this from the reaction system.
  • 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
  • the preferred reaction temperature varies depending on the type, molecular weight, polymerization temperature, etc. of the aromatic polycarbonate to be produced.
  • the number average molecular weight is less than 1000.
  • the range of ° C is preferable, and the range of 200 to 290 ° C is preferable when the temperature is 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.
  • 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, the range is 20 mmHg.
  • 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 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.
  • 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 very small part of the polymerization vessel or piping is in the temperature range of 180 ° C. to 220 ° C.
  • 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.
  • the production amount of polycarbonate and the molecular weight of polycarbonate can be adjusted.
  • 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.
  • 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 for discharging the polycarbonate from the polymerization vessel 100 may be branched into two to four.
  • 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.
  • 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.
  • a catalyst, a branching agent, or the like to the polycarbonate from the middle of the outlet pipe for further polymerization.
  • 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.
  • the difference between the heat medium outlet temperature and the heat medium inlet temperature of the equipment and piping (inlet-outlet) is preferably ⁇ 20 ° C. to 0.1 ° C., more preferably ⁇ 15 ° C. to 0.1 ° C., ⁇ It is more preferably 10 ° C. to 0.1 ° C., and particularly preferably ⁇ 5 ° C. to 0.1 ° C.
  • 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.
  • 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 vessel to a molding machine. Further, a polymer filter or the like having a filtration accuracy of about 1 to 50 ⁇ m may be installed in order to refine or remove the fish eye. 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.
  • a high-quality polycondensation reactive polymer having excellent molecular weight stability for example, an aromatic polycarbonate
  • the molecular weight distribution is small, and the color tone has an appropriate branching amount.
  • it is excellent in physical properties, and it is possible to reduce fish eyes caused by gel.
  • 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.
  • 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.
  • 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.
  • the arrangement of the wire guides 4 is as shown in (B), which is a schematic view showing the MM cross section of the polymerization vessel 200. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the guide may be a structure including at least a vertical wire, and is not limited to the wire guide 4.
  • a melted prepolymer with few foreign substances because a polymer with higher quality can be obtained.
  • a stirred tank type prepolymerizer (not shown) can be used.
  • a wire type nitrogen absorption facility (not shown) is used for the purpose of preliminarily absorbing nitrogen. Can also be used.
  • 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.
  • 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.
  • 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.
  • a filter see FIG. (Not shown) is preferably installed.
  • 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.
  • the pore diameter of the filter is preferably 0.05 to 3 mm smaller than the pore diameter of the polymer dispersion plate.
  • a hole diameter of 0.1 to 2 mm is more preferable, and a hole diameter of 0.1 to 1 mm is more preferable.
  • 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.
  • the discharge pipe can be washed with a raw material (for example, an aromatic monohydroxy compound).
  • a raw material for example, an aromatic monohydroxy compound.
  • the heat medium oil supplied from the heat medium boiler of the heating source when 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.
  • an inverted L-shaped elbow pipe part of a pipe for supplying a prepolymer to a main polymerizer such as a wire type.
  • a main polymerizer such as a wire type.
  • MPC 0.3591 ⁇ M PS 1.0388
  • MPC is the number average molecular weight or weight average molecular weight of the polymer
  • MPS is the number average molecular weight or weight average molecular weight of the standard monodisperse polystyrene.
  • 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.
  • 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.
  • the casing upper part 13a was cylindrical, and the casing bottom 13c was an inverted cone.
  • the casing body 13a has a cylindrical shape with an inner diameter of 1500 mm and a length of 10,000 mm.
  • 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.
  • 102 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 are provided in 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.
  • a plurality of polymer supply holes 12 through which the molten prepolymer flows are provided in 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.
  • 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 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.
  • 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 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.
  • 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%.
  • the output of the discharge pump 8 was controlled.
  • 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.
  • the supply amount of the molten prepolymer and the extraction amount of the aromatic polycarbonate were increased stepwise.
  • 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).
  • 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.
  • the branching amount was 0.26 mol%, and the number of fish eyes was 0.
  • Table 1 the viscosity value of the molten prepolymer is a value measured at 260 ° C.
  • fish eyes of 50 ⁇ m or more that can be visually observed were not observed.
  • the production amount of the aromatic polycarbonate was 600 kg / h, and the mass production was possible with high productivity.
  • Example 2 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.
  • Example 3 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.
  • Example 4 the wire guide which is not provided with the fixed wire was used. Further, L1 / L0 in Examples 2 to 10 and 13 was 1.00.
  • 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.
  • 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.
  • 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 are provided.
  • 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.
  • 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.
  • the hatched portion is a projection of a portion (Y) where the aromatic polycarbonate does not flow down
  • 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.
  • 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%.
  • the output of the discharge pump 8 was controlled.
  • 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 port 6 was 12800.
  • the number average molecular weight of the aromatic polycarbonate obtained every hour was measured.
  • the supply amount of the molten prepolymer and the extraction amount of the aromatic polycarbonate were increased stepwise.
  • 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.
  • a high-quality polycondensation reactive polymer having excellent molecular weight stability particularly an aromatic polycarbonate
  • 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 tone and physical properties.
  • 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).

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PCT/JP2015/056746 2014-03-19 2015-03-06 縮重合反応性ポリマー及びその製造装置 WO2015141501A1 (ja)

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EA201691665A1 (ru) 2017-02-28
JP6230695B2 (ja) 2017-11-15
KR20160084419A (ko) 2016-07-13
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