Aromatic branched polycarbonates, process for their production and apparatus for the production of aromatic branched polycarbonates

Abstract

An aromatic branched polycarbonate, wherein the aromatic branched polycarbonate has prescribed repeating units in a main chain and a branch chain, contains one or more prescribed branching structures in the main chain and the branch chain, a ratio of a total amount of substance of the branching structures with respect to an amount of substance of the prescribed repeating units is within a prescribed numerical range, the aromatic branched polycarbonate contains one or more prescribed oligomers, a total mass of the oligomers is within a prescribed numerical range, and a ratio of an amount of substance of an oligomer of a specific structure with respect to a total amount of substance of the oligomers is within a prescribed numerical range.

Description

TECHNICAL FIELD

[0001] The present application relates to an aromatic branched polycarbonate, a method for producing an aromatic branched polycarbonate, and an apparatus for producing an aromatic branched polycarbonate. BACKGROUND

[0002] In the past, as a method for producing an aromatic polycarbonate from an aromatic dihydroxy compound and a diaryl carbonate, for example, a melt method is known in which an aromatic dihydroxy compound (for example, bisphenol A) and a diaryl carbonate (for example, diphenyl carbonate) are subjected to an ester exchange reaction in a molten state, and polymerization is performed while extracting an aromatic monohydroxy compound (for example, phenol) produced.

[0003] However, the above ester exchange reaction is an equilibrium reaction, and the equilibrium constant thereof is small, and thus there are problems in that, as long as the aromatic monohydroxy compound produced is not effectively extracted from the surface of the melt, polymerization does not proceed. Also, there are problems in that, when polymerization proceeds to a certain extent, the viscosity of the polymer sharply rises, and it is difficult to effectively extract the aromatic monohydroxy compound produced to the outside of the system, and it is industrially impossible to produce a polymer having a degree of polymerization (n = about 30 to about 65) required as a product.

[0004] In view of the above problems, in order to achieve a degree of polymerization required as a product, for example, a method using a screw-type polymerizer having a vent portion (Japanese Patent Application Publication No. S50-19600 (corresponding to British Patent No. 1007302)), a method using a meshing-type double-screw extruder (Japanese Patent Application Publication No. S52-36159), and a method using a thin film evaporation-type reactor such as a screw evaporator or a centrifugal thin film evaporator (Japanese Patent Application Publication No. S53-5718 (corresponding to U.S. Patent No. 3,888,826)), and a method using a centrifugal thin film-type evaporation device in combination with a horizontal double-shaft stirring-type polymerizer (Japanese Patent Application Publication No. H02-153923) are known.

[0005] In these methods, an attempt is made to solve the above problems related to the degree of polymerization by increasing the polymerization temperature, and reducing the melt viscosity of the polymer. Specifically, while attempting to achieve surface renewal by mechanically stirring a molten prepolymer under high vacuum at a high temperature of about 300°C, polymerization is performed.

[0006] On the other hand, the present inventors have developed an industrial production method using a guide contact flow-down type polymerization device in which polymerization is performed while a molten prepolymer is caused to fall by its own weight along a guide member such as a wire, without mechanically stirring the molten prepolymer, and have proposed a technique that attempts to solve the problems of the above prior art (for example, refer to Patent Documents 1 and 2).

[0007] PRIOR ART DOCUMENTS

[0008] Patent Literature

[0009] Patent Literature 1: International Publication No. 2005 / 123805

[0010] Patent Literature 2: International Publication No. 2006 / 067994 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] However, even the methods disclosed in Patent Literatures 1 and 2 have the following problem: in order to achieve sufficient polymerization degree, it is necessary to increase the polymerization temperature to a high temperature of about 280°C, and there is room for improvement from the viewpoint of obtaining an aromatic polycarbonate having high thermal stability, less coloration, good color tone stability to heat, high quality, and high performance.

[0013] Therefore, an object of the present application is to provide an aromatic branched polycarbonate having less coloration and good color tone stability to heat.

[0014] MEANS FOR SOLVING THE PROBLEMS

[0015] The present inventors have conducted intensive studies in view of the problems of the above-described prior art, and as a result, have found that the above-described problems can be solved by an aromatic branched polycarbonate having prescribed repeating units in a main chain and a side chain, containing one or more prescribed branching structures in the above-described main chain and side chain, the ratio of the total amount of substance of the above-described branching structures to the amount of substance of the above-described prescribed repeating units being within a prescribed numerical range, containing one or more prescribed oligomers, the total mass of the above-described oligomers being within a prescribed numerical range, and the ratio of the total amount of substance of oligomers of a specific structure to the total amount of substance of the above-described oligomers being within a prescribed numerical range, thereby completing the present application.

[0016] That is, the present application is as described below. [1]

[0018] An aromatic branched polycarbonate, wherein the aromatic branched polycarbonate satisfies the following <Condition (i)> to <Condition (iii)>.

[0019] <Condition (i)>

[0020] has a repeating unit represented by the following general formula (1) in a main chain and a side chain,

[0021] contains one or more branching structures represented by the following general formulae (2), (3) and (4) in the main chain and side chain,

[0022] The ratio of the total amount of substance of the branching structure with respect to the amount of substance of the repeating unit represented by the following general formula (1) is 0.01 to 0.5 mol%.

[0023]

[0024] (In formulae (1), (2), (3), and (4), Ar represents a divalent aromatic group, and Ar' represents a trivalent aromatic group.)

[0025] <Condition (ii)>

[0026] The aromatic branched polycarbonate contains one or more oligomers represented by the following general formulae (5), (6), and (7), and the ratio of the total mass of the oligomers with respect to the mass of the aromatic branched polycarbonate is 0.6 mass% or less.

[0027] H-(O-Ar-O-C(=O)-)2-Oar" (5)

[0028] H-(O-Ar-O-C(=O)-)2-O-Ar-OH (6)

[0029] Ar"O-C(=O)-(O-Ar-O-C(=O)-)2-OAr" (7)

[0030] (In formulae (5), (6), and (7), Ar represents a divalent aromatic group, and Ar" represents an aromatic end group.)

[0031] <Condition (iii)>

[0032] The ratio of the total amount of substance of the oligomers represented by the above general formulae (5), (6) with respect to the total amount of substance of the oligomers is 60 mol% or less. [2]

[0034] The aromatic branched polycarbonate according to the above [1], wherein

[0035] In the above <Condition (i)>, the ratio of the total amount of substance of the branching structure with respect to the amount of substance of the repeating unit represented by the general formula (1) is 0.05 to 0.4 mol%,

[0036] In the above <Condition (ii)>, the ratio of the total mass of the oligomers with respect to the mass of the aromatic branched polycarbonate is 0.3 mass% or less,

[0037] In the above <Condition (iii)>, the ratio of the total amount of substance of the oligomers represented by the above general formulae (5), (6) with respect to the total amount of substance of the oligomers is 30 mol% or less. [3]

[0039] The aromatic branched polycarbonate according to any one of the above [1] to [2], wherein the MI (melt index) of the aromatic branched polycarbonate measured under conditions of a temperature of 300°C and a load of 1.2 kg is 0.5 g / 10 minutes to 40 g / 10 minutes. [4]

[0041] A method for producing an aromatic branched polycarbonate according to any one of the above [1] to [3], wherein the method for producing an aromatic branched polycarbonate is a method for producing an aromatic branched polycarbonate according to any one of the above [1] to [3], wherein

[0042] The method for producing an aromatic branched polycarbonate comprises the following steps:

[0043] The prepolymer of the aromatic branched polycarbonate which has absorbed nitrogen is maintained at 15 kPaA to 200 kPaA and supplied to a step of contacting a guide member constituting a production apparatus for the aromatic branched polycarbonate with a falling polymerization apparatus; and

[0044] The prepolymer is caused to fall along an outer surface of the guide member which does not have a heating source by itself, and a low-boiling substance is evaporated. [5]

[0046] The method for producing an aromatic branched polycarbonate according to the above [4], wherein the evaporation of the low-boiling substance is performed using a guide member contact falling polymerization apparatus, and the guide member contact falling polymerization apparatus satisfies the following <Condition (1)> to <Condition (9)>.

[0047] <Condition (1)>

[0048] The guide member contact falling polymerization apparatus has a liquid receiving port, a liquid supply zone for supplying a liquid to the guide member of an evaporation zone through a porous plate, an evaporation zone provided with a plurality of guide members extending downward from the porous plate in a space surrounded by the porous plate, a side surface case, and a bottom case, a vacuum exhaust port provided in the evaporation zone, and a liquid discharge port provided at the lowermost portion of the bottom case.

[0049] <Condition (2)>

[0050] A flow path control member having a function of causing a liquid supplied from the liquid receiving port to the porous plate to flow in a direction from the peripheral portion of the porous plate to the central portion in the liquid supply zone is provided in the liquid supply zone.

[0051] <Condition (3)>

[0052] The internal cross-sectional area A (m2) of the side surface case of the evaporation zone in the horizontal plane is 0.0005 A ≤ A ≤ 0.005 A.2 ) satisfies the following formula (I).

[0053] 0.7 ≤ A ≤ 300 Formula (I)

[0054] <Condition (4)>

[0055] The ratio of the internal cross-sectional area A (m 2 ) of the liquid discharge port to the internal cross-sectional area B (m 2 ) on the horizontal plane of the liquid discharge port satisfies the following formula (II).

[0056] 20 ≤ A / B ≤ 1000 Formula (II)

[0057] <Condition (5)>

[0058] The bottom shell constituting the bottom of the evaporation zone is connected to the side shell of the upper portion at an angle C degrees (°) inside the evaporation zone, and the angle C degrees satisfies the following formula (III).

[0059] 110 ≤ C ≤ 165 Formula (III)

[0060] <Condition (6)>

[0061] The length h (cm) of the guide satisfies formula (IV).

[0062] 150 ≤ h ≤ 5000 Formula (IV)

[0063] <Condition (7)>

[0064] The total external surface area S (m 2 ) of the plurality of guides as a whole satisfies formula (V).

[0065] 2 ≤ S ≤ 50000 Formula (V)

[0066] <Condition (8)>

[0067] The average number N (pieces / m 2 ) of holes per 1 m 2 ) of the perforated plate satisfies formula (VI).

[0068] 50 ≤ N ≤ 3000 Formula (VI)

[0069] <Condition (9)>

[0070] The ratio of the upper area T (m 2 ) of the perforated plate including the upper area of the holes of the perforated plate to the sum Q (m 2 ) of the effective cross-sectional areas of the holes satisfies the following formula (VII).

[0071] 50 ≤ T / Q ≤ 3000 Formula (VII) [6]

[0073] The method for producing an aromatic branched polycarbonate according to any one of the above [4] or [5], wherein the liquid after the evaporation treatment is 1 ton or more per 1 hour. [7]

[0075] The method for producing an aromatic branched polycarbonate according to any one of the above [5] or [6], wherein an angle E (°) formed by an inner side wall surface of the liquid supply zone and the perforated plate satisfies the following formula (VIII).

[0076] 100 ≤ E < 180 Formula (VIII) [8]

[0078] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to [7], wherein a distance K (cm) from the guide to an inner wall surface of the side shell closest to the evaporation zone satisfies the following formula (IX).

[0079] 5 ≤ K ≤ 50 Formula (IX) [9]

[0081] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to [8], wherein the side shell of the evaporation zone is a cylindrical shape with an inner diameter D (cm) and a length L (cm), a bottom shell connected to a lower portion of the side shell is a conical shape, a liquid discharge port at a lowermost portion of the conical bottom shell is a cylindrical shape with an inner diameter d (cm), and

[0082] the D, L, and d satisfy the following formulas (X), (XI), (XII), and (XIII).

[0083] 100 ≤ D ≤ 1800 Formula (X)

[0084] 5 ≤ D / d ≤ 50 Formula (XI)

[0085] 0.5 ≤ L / D ≤ 30 Formula (XII)

[0086] h-20 ≤ L ≤ h+300 Formula (XIII)

[0087] (In formula (XIII), h (cm) represents the length of the guide.)

[10]

[0089] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to [9], wherein a space volume V (m 3) the upper area T (m2) of the multiwell plate satisfies the following formula (XIII). 2 ) satisfies the following formula (XIV).

[0090] 0.02(m)≤V / T≤0.5(m) Formula (XIV)

[11]

[0092] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to

[10] , wherein at least one of the guides is a guide in a cylindrical shape having an outer diameter r (cm) or a tubular shape that does not allow liquid and / or gaseous substances to enter the inside of the guide, and

[0093] The outer diameter r satisfies the following formula (XV).

[0094] 0.1≤r≤1 Formula (XV)

[12]

[0096] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to

[11] , wherein the guide-contacting flow polymerization device has a plurality of the guides, and the plurality of guides are combined using a support material.

[13]

[0098] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to

[12] , wherein the plurality of guides are any one selected from the group consisting of a lattice-shaped or mesh-shaped guide obtained by fixing each guide using a support material in the lateral direction, a three-dimensional guide obtained by arranging a plurality of lattice-shaped or mesh-shaped guides in front and back and fixing these guides using a support material in the lateral direction, and a three-dimensional guide in the shape of a climbing frame obtained by fixing each guide of the plurality of guides in front and back and left and right using a support material in the lateral direction.

[14]

[0100] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to

[13] , wherein at least one guide-contacting flow polymerization device satisfying the above <Condition (1)> to <Condition (9)> is further connected to the guide-contacting flow polymerization device, and two or more of the guide-contacting flow polymerization devices are connected in any one of series, parallel, and a combination of series and parallel.

[15]

[0102] The method for producing an aromatic branched polycarbonate according to the above

[14] , wherein one guide-contacting flow polymerization device is further connected to the guide-contacting flow polymerization device, and the total outer surface area S1 (m2) of the guides of the guide-contacting flow polymerization devices satisfies the following formula (XVI).2 ) and the further connected guide member contacts an external total surface area S2 (m 2 ) satisfies the following formula (XVI).

[0103] 1≤S1 / S2≤20 (XVI)

[16]

[0105] The method for producing an aromatic branched polycarbonate according to any one of the above [5] to

[15] , wherein a non-active gas absorbing device for absorbing a non-active gas into a molten prepolymer of the aromatic branched polycarbonate before being supplied to the guide member contact flow down polymerization device is provided,

[0106] The pressure of the molten prepolymer absorbing the non-active gas in a supply pipe between the non-active gas absorbing device and the guide member contact flow down polymerization device is maintained at 15 kPaA to 200 kPaA by a pressure regulating valve provided immediately before the inlet of the guide member contact flow down polymerization device, and the molten prepolymer is supplied to the guide member contact flow down polymerization device.

[17]

[0108] The method for producing an aromatic branched polycarbonate according to the above

[15] or

[16] , wherein a guide member contact flow down polymerization device further connected to the guide member contact flow down polymerization device is provided,

[0109] A non-active gas absorbing device for absorbing a non-active gas into a molten prepolymer of the aromatic branched polycarbonate before being supplied to each of the guide member contact flow down polymerization devices is provided,

[0110] A pressure regulating valve is provided immediately before the inlet of each of the guide member contact flow down polymerization devices, and the pressure of the molten prepolymer absorbing the non-active gas in a supply pipe between the non-active gas absorbing device and each of the guide member contact flow down polymerization devices is maintained at 15 kPaA to 200 kPaA by the pressure regulating valve to supply the molten prepolymer.

[18]

[0112] A production device of an aromatic branched polycarbonate, the production device comprising:

[0113] a guide member contact flow down polymerization device that causes a prepolymer of the aromatic branched polycarbonate to flow down along an external surface of a guide member having no heating source thereof and evaporates a low-boiling substance during the flow down; and

[0114] An inactive gas absorbing device for absorbing an inactive gas from a molten prepolymer of an aromatic branched polycarbonate supplied to a guide contact flow polymerization device, wherein

[0115] The guide contact flow polymerization device satisfies the following <Condition (1)> to <Condition (9)>.

[0116] The manufacturing device has a function of controlling the pressure of the molten prepolymer in which the inactive gas is absorbed in a supply pipe of the molten prepolymer between the inactive gas absorbing device and the guide contact flow polymerization device to be 15 kPaA to 200 kPaA.

[0117] <Condition (1)>

[0118] The guide contact flow polymerization device has a liquid receiving port, a liquid supply area for supplying a liquid to the guide of an evaporation area through a porous plate, the evaporation area provided with a plurality of guides extending downward from the porous plate in a space surrounded by the porous plate, a side surface housing, and a bottom housing, a vacuum exhaust port provided in the evaporation area, and a liquid discharge port provided at the lowermost portion of the bottom housing.

[0119] <Condition (2)>

[0120] A flow path control member having a function of flowing a liquid supplied from the liquid receiving port to the porous plate in the liquid supply area from the peripheral portion of the porous plate to the central portion is provided in the liquid supply area.

[0121] <Condition (3)>

[0122] An internal cross-sectional area A (m 2 ) on a horizontal plane of the side surface housing of the evaporation area satisfies the following formula (I).

[0123] 0.7 ≤ A ≤ 300 Formula (I)

[0124] <Condition (4)>

[0125] A ratio of the internal cross-sectional area A (m 2 ) to an internal cross-sectional area B (m 2 ) on a horizontal plane of the liquid discharge port satisfies the following formula (II).

[0126] 20 ≤ A / B ≤ 1000 Formula (II)

[0127] <Condition (5)>

[0128] A bottom shell constituting a bottom of the evaporation zone is connected to a side shell of an upper portion inside the evaporation zone at an angle C degrees (°), and the angle C degrees satisfies the following formula (III).

[0129] 110 ≤ C ≤ 165 Formula (III)

[0130] <Condition (6)>

[0131] A length h (cm) of the guide satisfies the following formula (IV).

[0132] 150 ≤ h ≤ 5000 Formula (IV)

[0133] <Condition (7)>

[0134] A total external surface area S (m 2 ) of the plurality of guides as a whole satisfies the following formula (V).

[0135] 2 ≤ S ≤ 50000 Formula (V)

[0136] <Condition (8)>

[0137] An average number N (pieces / m 2 ) of the holes of the porous plate per 1 m 2 satisfies the following formula (VI).

[0138] 50 ≤ N ≤ 3000 Formula (VI)

[0139] <Condition (9)>

[0140] A ratio of an upper area T (m 2 ) of the porous plate including an upper area of the holes of the porous plate to a total Q (m 2 ) of effective cross-sectional areas of the holes satisfies the following formula (VII).

[0141] 50 ≤ T / Q ≤ 3000 Formula (VII)

[0142] Inventive Effects

[0143] According to the present application, it is possible to provide an aromatic branched polycarbonate having less coloration and good color tone stability to heat. BRIEF DESCRIPTION OF DRAWINGS

[0144] Figure 1 A schematic structural view showing a non-active gas absorbing device constituting a manufacturing device of an aromatic branched polycarbonate is shown.

[0145] Figure 2 A schematic structural view showing a guide contacting a falling polymerization device constituting a manufacturing device of an aromatic branched polycarbonate is shown.

[0146] Figure 3A schematic structural view showing the non-active gas absorbing device and the guide contacting the upper portion of the downflow type polymerization apparatus.

[0147] Figure 4 An enlarged schematic structural view showing the non-active gas absorbing device and the guide contacting the upper portion of the downflow type polymerization apparatus.

[0148] Figure 5 A schematic structural view showing an example of the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment. DETAILED DESCRIPTION

[0149] Hereinafter, a mode for carrying out the present application (hereinafter, also referred to as "the present embodiment") will be described in detail.

[0150] Note that the present application is not limited to the present embodiment, and can be carried out with various modifications within the scope of the gist thereof.

[0151] [Aromatic branched polycarbonate]

[0152] The aromatic branched polycarbonate of the present embodiment is an aromatic branched polycarbonate satisfying the following <Condition (i)> to <Condition (iii)>.

[0153] The aromatic branched polycarbonate of the present embodiment is manufactured by a transesterification method.

[0154] <Condition (i)>

[0155] has a repeating unit represented by the following general formula (1) in the main chain and the branched chain,

[0156] contains one or more branched structures represented by the following general formulas (2), (3) and (4) in the main chain and the branched chain,

[0157] a ratio of a total amount of substance of the branched structures to an amount of substance of the repeating unit represented by the following general formula (1) is 0.01 mol% to 0.5 mol%.

[0158]

[0159] (In formulas (1), (2), (3) and (4), Ar represents a divalent aromatic group, and Ar' represents a trivalent aromatic group.)

[0160] The trivalent aromatic group is, for example, a group in which one hydrogen atom in the above-described divalent aromatic group is a bonding point.

[0161] <Condition (ii)>

[0162] contains one or more oligomers represented by the following general formulae (5), (6) and (7) at a ratio of 0.6 mass% or less of the total mass of the oligomers with respect to the mass of the aromatic branched polycarbonate.

[0163] H-(O-Ar-O-C(=O)-)2-OAr" (5)

[0164] H-(O-Ar-O-C(=O)-)2-O-Ar-OH (6)

[0165] Ar"O-C(=O)-(O-Ar-O-C(=O)-)2-OAr" (7)

[0166] (In formulae (5), (6) and (7), Ar represents a divalent aromatic group, and Ar" represents an aromatic end group.)

[0167] <Condition (iii)>

[0168] The ratio of the total amount of substance of the oligomers represented by the above general formulae (5), (6) with respect to the total amount of substance of the oligomers is 60 mole% or less.

[0169] According to the present embodiment, it is possible to provide an aromatic branched polycarbonate which is less colored and has good color tone stability to heat.

[0170] From the viewpoint of maintaining the impact resistance of the aromatic branched polycarbonate of the present embodiment, the ratio of the total amount of substance of the branched structures represented by general formulae (2), (3) and (4) with respect to the amount of substance of the repeating unit represented by general formula (1) is 0.01 mole% to 0.5 mole%, preferably 0.05 mole% to 0.4 mole%, more preferably 0.1 mole% to 0.3 mole%, and further preferably 0.2 mole% to 0.25 mole%.

[0171] The ratio of the total amount of substance of the branched structures represented by general formulae (2), (3) and (4) with respect to the amount of substance of the repeating unit represented by general formula (1) can be measured by LC (liquid chromatography), and specifically, can be measured by the method described in the Examples below.

[0172] In addition, the ratio of the total amount of substance of the branched structures represented by general formulae (2), (3) and (4) with respect to the amount of substance of the repeating unit represented by general formula (1) can be controlled within the above numerical range by adjusting the polymerization conditions.

[0173] The purity of the aromatic branched polycarbonate of the present embodiment having the repeating unit represented by General Formula (1) in the main chain and the branched chain, and containing one or more branching structures represented by General Formulas (2), (3), and (4) in the main chain and the branched chain is preferably 80% by mass or more, preferably 90% by mass or more, preferably 95% by mass or more, and more preferably 98% by mass or more.

[0174] As described above, the aromatic branched polycarbonate of the present embodiment contains one or more oligomers represented by General Formulas (5), (6), and (7) below, and the ratio of the total mass of the oligomers with respect to the mass of the aromatic branched polycarbonate is 0.6% by mass or less.

[0175] H-(O-Ar-O-C(=O)-)2-OAr" (5)

[0176] H-(O-Ar-O-C(=O)-)2-O-Ar-OH (6)

[0177] Ar"O-C(=O)-(O-Ar-O-C(=O)-)2-OAr" (7)

[0178] (In Formulas (5), (6), and (7), Ar represents a divalent aromatic group, and Ar" represents an aromatic end group.)

[0179] As the aromatic end group, a monovalent aromatic group having 5 to 20 carbon atoms can be exemplified.

[0180] By the ratio of the total mass of the above-described oligomers with respect to the mass of the aromatic branched polycarbonate being 0.6% by mass or less, the color tone stability to heat is excellent. The above-described ratio is preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and further preferably 0.3% by mass or less. In addition, the above-described ratio is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.

[0181] The ratio of the total mass of the oligomers represented by the above-described General Formulas (5), (6), and (7) can be measured by GPC (gel permeation chromatography), and specifically, can be measured by the method described in the Examples below.

[0182] In addition, the ratio of the total mass of the oligomers represented by General Formulas (5), (6), and (7) can be controlled within the above-described numerical range by polymerizing using a polymerization device described below using a guide, and by supplying a prepolymer supplied to the device after absorbing nitrogen gas and maintaining the pressure described below.

[0183] The ratio of the total amount of substance of the oligomers represented by general formulae (5) and (6) to the total amount of substance of the oligomers represented by general formulae (5), (6), and (7) is 60 mol% or less.

[0184] By the ratio of the total amount of substance of the oligomers represented by general formulae (5) and (6) to the total amount of substance of the oligomers represented by general formulae (5) to (7) being within the above range, an aromatic branched polycarbonate having little coloring and good hue stability to heat can be obtained.

[0185] The above ratio is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the above ratio is not particularly limited and can be set to 10 mol% or more.

[0186] The ratio of the total amount of substance of the oligomers represented by general formulae (5) and (6) to the total amount of substance of the oligomers represented by general formulae (5), (6), and (7) can be measured by GPC (gel permeation chromatography), and specifically, can be measured by the method described in the Examples below.

[0187] In addition, the ratio of the total amount of substance of the oligomers represented by general formulae (5) and (6) to the total amount of substance of the oligomers represented by general formulae (5), (6), and (7) can be controlled within the above numerical range by performing polymerization using a polymerization device described below with a guide, and by feeding a prepolymer supplied to the device after absorbing nitrogen gas and maintaining it at a prescribed pressure described below.

[0188] In the above formula, Ar represents a divalent aromatic group.

[0189] The divalent aromatic group Ar is preferably, for example, a group represented by the following formula.

[0190] -Ar 1 -Y-Ar 2 -

[0191] (In the formula, Ar 1 and Ar 2 each independently represents a divalent carbon ring or heterocyclic aromatic group having 5 to 70 carbon atoms, and Y represents a divalent alkane group having 1 to 30 carbon atoms.)

[0192] The divalent aromatic group Ar 1 , Ar 2More than one hydrogen atom can be replaced with other substituents such as halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, nitro groups, and the like, which do not adversely affect the reaction. As the heterocyclic aromatic group, there can be mentioned, for example, an aromatic group having one to several ring-forming nitrogen atoms, oxygen atoms, or sulfur atoms.

[0193] As the divalent aromatic group Ar 1 , Ar 2 For example, there can be mentioned substituted or unsubstituted phenylene groups, substituted or unsubstituted biphenylene groups, substituted or unsubstituted pyridylene groups, and the like. The substituents herein are as described above.

[0194] The divalent alkane group Y is, for example, an organic group represented by the following formula.

[0195]

[0196] (In the above formula, R 1 , R 2 , R 3 , R 4 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring-forming carbon atoms, a carbocyclic aromatic group having 5 to 10 ring-forming carbon atoms, or a carbocyclic aralkyl group having 6 to 10 carbon atoms.

[0197] k represents an integer of 3 to 11, and R 5 and R 6 each of X is independently selected from the group consisting of hydrogen and an alkyl group having 1 to 6 carbon atoms, and X represents carbon.

[0198] In addition, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 More than one hydrogen atom can be replaced with other substituents such as halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, nitro groups, and the like, which do not adversely affect the reaction.

[0199] As such a divalent aromatic group Ar, for example, there can be mentioned a group represented by the following formula.

[0200]

[0201] (In the above formula, R 7 , R 8each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyclic alkyl group having 5 to 10 ring-forming carbon atoms, or a phenyl group, m and n are integers of 1 to 4, in the case where m is 2 to 4, each R 7 each can be the same or different, in the case where n is 2 to 4, R 8 each can be the same or different.

[0202] Further, the divalent aromatic group Ar can be a group represented by the following formula.

[0203] -Ar 1 -Z-Ar 2 -

[0204] (in the formula, Ar 1 and Ar 2 As described above, Z represents a single bond or a divalent group of -0-, -CO-, -S-, -SO2-, -SO-, -COO-, -CON(R 1 )-, and the like. Note that R 1 As described above.) As such a divalent aromatic group Ar, for example, a group represented by the following formula can be cited.

[0205]

[0206] (in the above formula, R 7 , R 8 , m, and n are as described above.)

[0207] Further, as a specific example of the divalent aromatic group Ar, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, and the like can be cited.

[0208] In the above formulae (2) to (4), Ar' represents a trivalent aromatic group. The trivalent aromatic group is, for example, a group in which one hydrogen atom in the above-described divalent aromatic group is a bonding point.

[0209] In the above formulae (5) to (7), Ar" represents a monovalent carbon ring or heterocyclic aromatic terminal group. As the aromatic terminal group, a monovalent aromatic group having 5 to 20 carbon atoms can be cited as a preferable aromatic terminal group.

[0210] In the above formulae (5) to (7), Ar" represents a monovalent carbon ring or heterocyclic aromatic group as described above, and Ar" can be a group in which one or more hydrogen atoms are substituted with another substituent such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group, or the like, which do not adversely affect the reaction. Ar" can be the same or different. As the monovalent aromatic group Ar", for example, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, and the like can be exemplified. They can be substituted with one or more of the above-mentioned substituents.

[0211] As the preferred Ar", each can be exemplified by a group represented by the following formulae, and the like.

[0212]

[0213] As a raw material for producing the aromatic branched polycarbonate of the present embodiment, a diaryl carbonate is used. As the diaryl carbonate, for example, a substituted or unsubstituted diphenyl carbonate represented by the following formulae can be exemplified.

[0214]

[0215] (In the above formulae, R 9 and R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring-forming carbon atoms, or a phenyl group, and p and q are integers of 1 to 5. In the case where p is 2 or more, each R 9 each can be different, and in the case where q is 2 or more, each R 10 each can be different.)

[0216] From the viewpoint of moldability, the MI (melt index) of the aromatic branched polycarbonate of the present embodiment, which is measured under the conditions of a temperature of 300°C and a load of 1.2 kg, is preferably 0.5 g / 10 minutes to 40 g / 10 minutes. More preferably, it is 0.5 g / 10 minutes to 20 g / 10 minutes, further preferably 1 g / 10 minutes to 15 g / 10 minutes, further more preferably 2 g / 10 minutes to 12 g / 10 minutes. In the case where the MI is in the range of 0.5 g / 10 minutes to 20 g / 10 minutes, the moldability and the drawdown property are further improved. The MI can be measured by the method described in the Examples described later.

[0217] In the aromatic branched polycarbonate of the present embodiment, it is preferable that the aromatic branched polycarbonate contain substantially no impurities, and it is preferable that the aromatic branched polycarbonate contain 0.001 ppm to 1 ppm of an alkali metal and / or an alkaline earth metal, in terms of metal elements. The content is preferably 0.005 ppm to 0.5 ppm, more preferably 0.01 ppm to 0.1 ppm.

[0218] In the case where the metal element is 1 ppm or less, preferably 0.5 ppm or less, more preferably 0.1 ppm or less, there is no influence on the physical properties of the aromatic branched polycarbonate as a product. The above content of the alkali metal and / or the alkaline earth metal can be achieved by manufacturing using the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment described later. The above content of the alkali metal and / or the alkaline earth metal can be measured by IPC (inductively coupled plasma) analysis.

[0219] The halogen content in the aromatic branched polycarbonate of the present embodiment is preferably 10 ppb or less, more preferably 5 ppb or less, further preferably 1 ppb or less. The halogen content can be achieved by manufacturing using the raw material described later and using the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment. The halogen content can be measured by IPC (inductively coupled plasma) analysis.

[0220] [Method for manufacturing aromatic branched polycarbonate]

[0221] The method for manufacturing the aromatic branched polycarbonate of the present embodiment has the following steps:

[0222] The prepolymer of the aromatic branched polycarbonate which has absorbed nitrogen is maintained at 15 kPaA to 200 kPaA, and is supplied to a step of contacting a guide member constituting the manufacturing apparatus for the aromatic branched polycarbonate to a falling polymerization apparatus; and

[0223] The above prepolymer is caused to fall along the outer surface of the guide member which does not have a heating source itself, and a low-boiling substance is evaporated.

[0224] By adjusting the prepolymer to the range of 15 kPaA to 200 kPaA, it is easy to obtain the aromatic branched polycarbonate satisfying the above <Condition (ii)> and <Condition (iii)>. In addition, by polymerizing using the guide member contacting falling polymerization apparatus, it is possible to reduce the melt flow index (MI), and in addition, it is possible to reduce the variation of the MI after the start of manufacturing, and it is possible to suppress the standard deviation of the MI to be low.

[0225] Note that the low-boiling substance is a substance having a lower boiling point than the target aromatic branched polycarbonate which is generated as a by-product in the manufacturing step.

[0226] The pressure of the prepolymer is preferably in the range of 15 to 200 kPaA, more preferably 20 to 150 kPaA, and further preferably 20 to 100 kPaA, from the viewpoint of obtaining an aromatic branched polycarbonate satisfying the above-mentioned <Condition (ii)> and <Condition (iii)>.

[0227] In the apparatus for producing an aromatic branched polycarbonate described later in this embodiment, in order to maintain the pressure of the prepolymer absorbing the inactive gas in the pipe between the inactive gas absorbing apparatus and the inlet of the leader contact flow down polymerization apparatus at a predetermined pressure, it is preferable to provide a predetermined pressure regulating valve immediately before the inlet of the leader contact flow down polymerization apparatus.

[0228] The inside of the leader contact flow down polymerization apparatus is under a high vacuum, and the prepolymer in the vicinity of the liquid receiving port of the leader contact flow down polymerization apparatus is sucked by the leader contact flow down polymerization apparatus, and is easily brought to a state of low pressure. Therefore, the inactive gas absorbed in the inactive gas absorbing apparatus is sometimes separated from the prepolymer and aggregated. Therefore, in order to prevent the separation and aggregation of the inactive gas, the pressure of the prepolymer is preferably in the above-mentioned numerical range.

[0229] In detail, the pressure in the pipe between the gear pump under the inactive gas absorbing apparatus and the leader contact flow down polymerization apparatus is maintained at a high pressure (normal pressure to 15 kPaA or more) up to the vicinity immediately before the leader contact flow down polymerization apparatus due to pressure loss of the pipe or the like. Therefore, it is preferable to maintain the pressure at 15 kPaA or more only immediately before entering the leader contact flow down polymerization apparatus.

[0230] In the case where the prepolymer is supplied to the leader contact flow down polymerization apparatus at a pressure lower than 15 kPaA immediately before the inlet of the leader contact flow down polymerization apparatus, it is possible that the pressure of the prepolymer in the upper portion of the perforated plate becomes unstable, the gas inactive gas such as nitrogen temporarily absorbed by the prepolymer is separated or aggregated, and the uniformity of the prepolymer becomes unstable, thereby hindering uniform and continuous foaming of the prepolymer in the leader contact flow down polymerization apparatus, and a stable product cannot be produced; or a decrease in color tone, fisheyes, gels, and the like are easily produced.

[0231] Therefore, in the case where the pressure of the prepolymer cannot be maintained at 15 kPaA or more, it is preferable to provide a pressure regulating valve or the like, thereby regulating the pressure of the prepolymer to 15 kPaA or more.

[0232] On the other hand, even if the pressure of the prepolymer exceeds 200 kPaA, the effect does not change, and an excessive load is applied to the discharge gear pump and the pipe of the inactive gas absorbing apparatus, and it is necessary to improve the pressure resistance, which is not realistic.

[0233] Therefore, the pressure at which the prepolymer is supplied to the guide contact flow polymerization device is preferably within the above numerical range.

[0234] [Manufacturing device used in manufacturing method of aromatic branched polycarbonate]

[0235] Hereinafter, the specific structure of the manufacturing device of the aromatic branched polycarbonate of the present embodiment used in the manufacturing method of the aromatic branched polycarbonate of the present embodiment will be described with reference to the accompanying drawings.

[0236] Figure 5 A schematic structural diagram of an example of the manufacturing device of the aromatic branched polycarbonate of the present embodiment is shown in FIG. 1.

[0237] In the manufacturing device of the aromatic branched polycarbonate, the polymerization raw material and the catalyst are put into and mixed in a mixing tank 31, and then transported to a dissolving mixture storage tank 33A, 33B using a transport pump 32, and further pre-polymerized in a first polymerizer 35 using transport pumps 34A, 34B from the storage tank 33A, 33B.

[0238] Then, pre-polymerization is performed in a second polymerizer 37 via a discharge gear pump 36, and thus a prepolymer of the aromatic branched polycarbonate is obtained.

[0239] The prepolymer of the aromatic branched polycarbonate is transported to a first inactive gas absorption device 39 via a supply pump 38, the solubility of the inactive gas is adjusted using a pressure regulating valve 41, transported to a first guide contact flow polymerization device 42 via a supply pump 40, and polymerized. Here, phenol, which is a low molecular weight component, is discharged from the exhaust port as a low-boiling substance.

[0240] Then, transported to a second inactive gas absorption device 44 via a supply pump 43, and then branched from here using a three-way polymer valve 45, and transported using supply pumps 46A, 46B. The solubility of the inactive gas is adjusted using pressure regulating valves 47A, 47B, transported to the connected second guide contact flow polymerization devices 48A, 48B, and polymerized. Here, phenol is discharged from the exhaust port.

[0241] Then, transported using supply pumps 49A, 49B, and additives are added in the devices 50A, 50B in the latter stage, and thus the target aromatic branched polycarbonate is obtained.

[0242] Note that, regarding the pressure regulating valves 41, 47A, 47B that adjust the solubility of the inactive gas, there is no limitation on the form thereof, and it can be a valve provided on a prescribed pipe, or it can be another device capable of controlling a prescribed pressure.

[0243] In the production method of the aromatic branched polycarbonate of the present embodiment, evaporation of the low-boiling-point substance is performed using a guide-contacting flow-down type polymerization apparatus that satisfies the following <Condition (1)> to <Condition (9)>.

[0244] Figure 1 A schematic structural diagram of the non-active gas absorption apparatus 39, 44 is shown in FIG. 1, Figure 2 A schematic structural diagram of the guide-contacting flow-down type polymerization apparatus 42, 48A, 48B is shown in FIG. 2.

[0245] Note that the non-active gas absorption apparatus and the guide-contacting flow-down type apparatus differ in that the non-active gas absorption apparatus has a non-active gas absorption zone in the internal space thereof for performing absorption of non-active gas, and the guide-contacting flow-down type apparatus has an evaporation zone in the internal space thereof for performing evaporation of the low-boiling-point substance, but the basic apparatus structure is common.

[0246] Figure 3 and Figure 4 A schematic diagram of the upper portion of the non-active gas absorption apparatus and the guide-contacting flow-down type polymerization apparatus is shown in FIG. 3.

[0247] The production apparatus of the aromatic branched polycarbonate of the present embodiment preferably has the guide-contacting flow-down type polymerization apparatus that satisfies the following <Condition (1)> to <Condition (9)>.

[0248] <Condition (1)>

[0249] The guide-contacting flow-down type polymerization apparatus has a liquid receiving port 1, a liquid supply zone 3 for supplying liquid to the guide 4 of the evaporation zone 5 through the porous plate 2, an evaporation zone 5 provided with a plurality of guides 4 extending downward from the porous plate 2 in a space surrounded by the porous plate 2, the side surface housing 10, and the bottom housing 11, a vacuum exhaust port 6 provided in the evaporation zone 5, and a liquid discharge port 7 provided at the lowermost portion of the bottom housing.

[0250] <Condition (2)>

[0251] A flow path control member 20 is provided in the liquid supply zone 3, and the flow path control member 20 has a function of flowing the liquid supplied from the liquid receiving port 1 to the porous plate 2 in the liquid supply zone 3 in a direction from the peripheral portion of the porous plate 2 to the central portion.

[0252] <Condition (3)>

[0253] The internal cross-sectional area A (m2) on the horizontal plane of the side surface housing 10 of the evaporation zone 5 (cutting plane at a-a' in FIG. 4) satisfies the following formula (I). Figure 2 In the formula (I), a is the distance from the center of the evaporation zone 5 to the center of the guide 4, and b is the distance from the center of the evaporation zone 5 to the center of the porous plate 2. 2 ) satisfies the following formula (I).

[0254] 0.7≤A≤300 Formula (I)

[0255] <Condition (4)>

[0256] The internal cross-sectional area A (m 2 ) and the horizontal plane of the liquid outlet 7 Figure 2 In the middle, the internal cross-sectional area B (m) on the b-b' surface) 2 The ratio of ) satisfies equation (II).

[0257] 20≤A / B≤1000 Equation (II)

[0258] By satisfying equation (II) above, it is possible to discharge the melt with increased melt viscosity without reducing the quality of the evaporated and concentrated liquid or polymer, or the polymer produced.

[0259] <Condition (5)>

[0260] The bottom shell 11, which forms the bottom of the evaporation zone 5, is located inside the evaporation zone 5. Figure 2 The middle part is connected to the upper side shell 10 by an angle C (°), and the angle C preferably satisfies formula (III).

[0261] 110≤C≤165 Equation (III)

[0262] To reduce equipment costs, C should be as close to 90 degrees as possible. However, in order to move the molten material with increased melt viscosity to the outlet 7 without reducing the quality of the concentrated liquid or polymer falling from the lower end of the guide 4, C preferably satisfies formula (III).

[0263] <Condition (6)>

[0264] The length h (cm) of the guide 4 satisfies equation (IV).

[0265] Equation (IV) 150≤h≤5000

[0266] With a length h of 150 cm or more, concentration or polymerization can be carried out at a practically sufficient speed and quality. With a length h of 5000 cm or less, the viscosity difference between the upper and lower parts of the liquid in the guide 4 will not be too large, thus preventing changes in the degree of concentration or polymerization.

[0267] <Condition (7)>

[0268] The total external surface area S(m²) of the plurality of guides 4 2 It satisfies the following equation (V).

[0269] 2≤S≤50000 Equation (V)

[0270] Through S(m) 2 With a value of 2 or higher, it can achieve a production volume of more than 1 ton of evaporated liquid per hour and a production volume of polymer.

[0271] Additionally, S(m) 2 With a capacity of less than 50,000, this production volume can be achieved while reducing equipment costs and maintaining the same material properties.

[0272] <Condition (8)>

[0273] per 1m 2 The average number of holes N (holes / m) in the perforated plate 2 Satisfy equation (VI).

[0274] Equation (VI) 50≤N≤3000

[0275] Average number of holes N (holes / m) in a perforated plate 2 T(m²) refers to the total number of holes divided by the area of ​​the upper surface of the perforated plate 2 (including the area above the holes). 2 The value obtained is ).

[0276] The holes in the porous plate 2 are preferably arranged substantially uniformly. However, the distance K (cm) between the periphery of the porous plate 2 and the inner wall of the evaporation zone 5 is generally preferably longer than the distance between adjacent holes. Therefore, the number of holes per unit area at the periphery is preferably less than the number of holes per unit area at the center. In this embodiment, the average number of holes N is used in this sense. More preferably, N is in the range of 70 ≤ N ≤ 2000, and even more preferably, N is in the range of 100 ≤ N ≤ 1000.

[0277] <Condition (9)>

[0278] The upper area T(m²) of the porous plate, including the upper area of ​​the holes in the porous plate. 2 The sum of Q(m) and the effective cross-sectional area of ​​the hole 2 The ratio of ) satisfies the following equation (VII).

[0279] 50≤T / Q≤3000 Equation (VII)

[0280] The T / Q ratio is more preferably 100 to 2500, and even more preferably 250 to 1500.

[0281] It should be noted that the "effective cross-sectional area" of the orifice in a perforated plate refers to the area of ​​the narrowest part of the cross-section through which the liquid passes. When the guide 4 penetrates the orifice, the "effective cross-sectional area" is the area obtained by subtracting the cross-sectional area of ​​the guide 4 from the cross-sectional area of ​​the orifice.

[0282] Q(m2 ) represents the sum of the effective cross-sectional areas of these holes.

[0283] In order to continuously and stably perform evaporation treatment of a large amount of liquid, particularly a liquid having high viscosity, for a long period of time, the above Formulas (VI) and (VII) are important.

[0284] The manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment, which satisfies the above configuration, not only solves the problems of the conventionally known evaporation apparatuses, but also stably manufactures a non-stained high-quality and high-performance concentrated liquid or polymer, i.e., a liquid subjected to evaporation treatment, in an amount of 1 ton or more per 1 hour for a long period of time of several thousand hours or more, for example, 5,000 hours or more.

[0285] The manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment has such an excellent effect because, in addition to the above various reasons, a synergistic effect brought about when these conditions are combined is exhibited.

[0286] For example, the high-surface-area guide satisfying the above Formulas (IV) and (V) is very effective for efficient internal stirring and surface renewal of a large amount of liquid, a prepolymer, or a polymer supplied at a lower temperature, can efficiently perform evaporation of a low-boiling-point substance, contributes to obtaining a high-quality concentrated liquid or polymer in a large amount of 1 ton or more per 1 hour, and the angle C satisfying the above Formula (III) can shorten the time until a large amount of high-quality concentrated liquid or polymer falling from the guide 4 is discharged from the liquid discharge port 7, and reduce the heat history.

[0287] Note that the performance of the guide-contacted flow-down type polymerization apparatus of an industrial scale is established by long-time operation using a large-scale manufacturing apparatus, but the manufacturing apparatus cost at this time is an important factor to be considered.

[0288] Compared with the conventional evaporation apparatus or polymerizer, the guide-contacted flow-down type polymerization apparatus constituting the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment can reduce the apparatus cost relative to the performance.

[0289] The ranges required for the specific conditions, dimensions / angles, etc. of the guide-contacted flow-down type polymerization apparatus of the present embodiment are as described above, and more preferable ranges are as described below.

[0290] The internal cross-sectional area A (m2) on the horizontal plane of the side housing 10 of the evaporation zone 5 shown in Formula (I) is more preferably in the range of 0.8 ≤ A ≤ 250, and further preferably in the range of 1 ≤ A ≤ 200. 2 The internal cross-sectional area A (m2) on the horizontal plane of the side housing 10 of the evaporation zone 5 shown in Formula (I) is more preferably in the range of 0.8 ≤ A ≤ 250, and further preferably in the range of 1 ≤ A ≤ 200.

[0291] In addition, the internal cross-sectional area A (m2) on the horizontal plane of the side housing 10 of the evaporation zone 5 shown in Formula (II) is more preferably in the range of 0.8 ≤ A ≤ 250, and further preferably in the range of 1 ≤ A ≤ 200. 2 The internal cross-sectional area A (m2) on the horizontal plane of the side housing 10 of the evaporation zone 5 shown in Formula (I) is more preferably in the range of 0.8 ≤ A ≤ 250, and further preferably in the range of 1 ≤ A ≤ 200.2 A / B is more preferably in the range of 25≤A / B≤900, further preferably in the range of 30≤A / B≤800.

[0292] Further, the angle C (°) formed by the bottom housing 11 constituting the bottom of the evaporation zone 5 and the upper side housing 10 inside the evaporation zone 5 is more preferably in the range of 120≤C≤165, further preferably in the range of 135≤C≤165. Note that in the case where the concentration or polymerization degree is sequentially increased using a plurality of guides, if the respective angles are set as C1, C2, C3,..., it is preferable that C1≤C2≤C3≤...

[0293] Further, the length h (cm) of the guide 4 required by the formula (IV) differs depending on the amount or viscosity or temperature of the liquid to be treated, the amount or boiling point of the low-boiling substance, the pressure or temperature of the evaporation zone, the required concentration or polymerization degree, and the like, and is more preferably in the range of 200≤h≤3000, further preferably in the range of 400≤h≤2500.

[0294] Further, the total external surface area S (m2) of the guide as a whole required by the formula (V) also differs depending on the same factors as described above, and is more preferably in the range of 10≤S≤40000, further preferably in the range of 15≤S≤30000. 2

[0295] In the present specification, the total external surface area of the guide as a whole refers to the entire surface area of the guide that the liquid contacts and flows down, and for example, in the case of a pipe or the like as the guide, the total external surface area of the guide as a whole refers to the surface area on the outside, and does not include the surface area of the inside of the pipe that does not cause the liquid to flow down.

[0296] As shown in FIG. 1, the liquid receiving port 1 is preferably provided at the upper portion of the liquid supply zone 3. Figures 1-3 The liquid receiving port 1 can be one or a plurality of ports, and is preferably configured to supply the liquid to the multi-well plate 2 as evenly as possible in the liquid supply zone 3. In the case where the liquid receiving port 1 is one, it is preferably provided at the central portion of the upper portion of the liquid supply zone 3.

[0297]

[0298] ​​Preferably, a flow path control member 20 is provided in the liquid supply area 3, and the flow path control member 20 has a function of causing the liquid supplied from the liquid receiving port 1 to the porous plate 2 in the liquid supply area 3 to flow mainly in a direction from the peripheral portion to the central portion of the porous plate 2. By providing the flow path control member 20, the liquid is caused to flow from the peripheral portion to the central portion of the porous plate 2, thereby having an effect of preventing the liquid from being long-stayed in a space between the hole portion (e.g., 21) of the porous plate 2 and the inner side wall surface 22 of the liquid supply area. The liquid flowing mainly from the peripheral portion to the central portion of the porous plate 2 is supplied from the hole of the porous plate 2 present therebetween to the guide 4.

[0299] As for the shape of the flow path control member 20, any shape can be adopted as long as the effect thereof can be exerted, and the outer shape of the cross section thereof is preferably similar to the outer shape of the cross section of the porous plate 2. Here, the cross section of the flow path control member 20 refers to a portion that exhibits the largest area when the flow path control member 20 is cut with a face in the lateral direction.

[0300] The interval between the flow path control member 20 and the inner side wall surface 22 of the liquid supply area 3 is preferably in a range different depending on the amount, viscosity, and the like of the liquid to be treated, and in the guide contacting flow down type polymerization device, the non-active gas absorbing device, which constitute the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment, in the case where the viscosity of the liquid to be treated is high, it is generally preferable to be in a range of 1 cm to 50 cm, more preferably 2 cm to 30 cm, and further preferably 3 cm to 20 cm.

[0301] As shown in Figs. 1 and 2, the flow path control member 20 is provided in the liquid supply area 3, and the flow path control member 20 has a function of causing the liquid supplied from the liquid receiving port 1 to the porous plate 2 in the liquid supply area 3 to flow mainly in a direction from the peripheral portion to the central portion of the porous plate 2. By providing the flow path control member 20, the liquid is caused to flow from the peripheral portion to the central portion of the porous plate 2, thereby having an effect of preventing the liquid from being long-stayed in a space between the hole portion (e.g., 21) of the porous plate 2 and the inner side wall surface 22 of the liquid supply area. The liquid flowing mainly from the peripheral portion to the central portion of the porous plate 2 is supplied from the hole of the porous plate 2 present therebetween to the guide 4. Figure 3 and Figure 4 As shown in Figs. 1 and 2, the flow path control member 20 is provided in the liquid supply area 3, and the flow path control member 20 has a function of causing the liquid supplied from the liquid receiving port 1 to the porous plate 2 in the liquid supply area 3 to flow mainly in a direction from the peripheral portion to the central portion of the porous plate 2. By providing the flow path control member 20, the liquid is caused to flow from the peripheral portion to the central portion of the porous plate 2, thereby having an effect of preventing the liquid from being long-stayed in a space between the hole portion (e.g., 21) of the porous plate 2 and the inner side wall surface 22 of the liquid supply area. The liquid flowing mainly from the peripheral portion to the central portion of the porous plate 2 is supplied from the hole of the porous plate 2 present therebetween to the guide 4.

[0302] As for the interval between the upper inner wall surface 23 of the liquid supply area 3 and the flow path control member 20, the flow path control member 20 in which the interval from the liquid receiving port 1 to the inner side wall surface 22 of the liquid supply area 3 is substantially the same can be adopted, and the flow path control member 20 in which the interval is gradually narrowed or, on the contrary, gradually widened can be adopted.

[0303] In addition, the interval between the flow path control member 20 and the porous plate 2 is generally 1 cm to 50 cm, preferably 2 cm to 30 cm, and more preferably 3 cm to 20 cm.

[0304] The gap between the multi-well plate 2 and the flow path control member 20 can be set to be substantially the same from the inner side wall surface 22 of the liquid supply area 3 to the central portion of the multi-well plate 2, or can be set so that the gap gradually narrows or, conversely, gradually widens. It is preferable to use a flow path control member 20 that is substantially the same or gradually narrows.

[0305] The flow path control member 20 described above obstructs the liquid supplied from the liquid receiving port 1 from being directly introduced into the wells of the multi-well plate 2, and thus functions as a kind of baffle. Note that in the case where the area of the multi-well plate 2 is large, it is also preferable for a portion of the supplied liquid to short-circuit near the central portion of the multi-well plate 2 without passing through the peripheral portion of the multi-well plate 2, and thus it is also preferable to provide one or more holes near the central portion of the flow path control member 20 or another appropriate portion.

[0306] In order to prevent the formation of a "dead zone" in the liquid supply area 3, it is further preferable for the angle formed by the inner side wall surface 22 of the liquid supply area and the multi-well plate 2, i.e., the E degrees (°) in Figure 4 satisfy the following equation (VIII):

[0307] 100 ≤ E < 180 Equation (VIII)

[0308] Here, in the case where the inner side wall surface 22 of the liquid supply area 3 described above is planar, the angle formed by the inner side wall surface 22 and the multi-well plate 2 in a cutting surface that is perpendicular to the plane and perpendicular to the upper surface of the multi-well plate 2 is E degrees (°).

[0309] In addition, in the case where the inner side wall surface 22 described above is a curved surface of a concave face, the angle formed by the tangent line at the point where the curve formed in a cutting surface that is perpendicular to the concave face and perpendicular to the upper surface of the multi-well plate 2 begins to rise and the upper surface of the multi-well plate 2 is E degrees (°).

[0310] It is more preferable for the range of E degrees (°) to be 120 ≤ E < 180, and further preferable to be 145 ≤ E < 180.

[0311] In addition, it is also preferable to design the liquid supply area 3 so that a "dead zone" is not formed near the joint between the upper inner wall surface 23 and the inner side wall surface 22, and it is preferable for the angle formed by these two surfaces to be greater than 90°, or in the case where it is 90° or close to 90°, to form the joint in a concave shape so that the liquid does not stagnate.

[0312] In the apparatus for producing an aromatic branched polycarbonate of the present embodiment, it is preferable for the distance K (cm) from the inner wall surface of the side housing 10 closest to the evaporation zone 5 to the guide 4 to satisfy the following equation (IX).

[0313] 5 ≤ K ≤ 50 Equation (IX)

[0314] When liquid adheres to the inner wall surface of the side shell 10 of the evaporation zone 5 described above, evaporation concentration occurs on the inner wall surface, and the concentrated liquid flows down along the inner wall surface. However, the inner wall surface is usually heated by steam or a heat medium using a jacket or the like or by an electric heater or the like for the purpose of heat insulation and / or heating of the evaporation zone 5, and thus the liquid adhering to the inner wall surface is highly concentrated and usually has a high viscosity compared to the liquid flowing down along the guide 4. The time (residence time) for the liquid with a high viscosity to flow down along the wall surface becomes long, and the viscosity becomes higher.

[0315] Furthermore, heating is usually continuously performed from the outer wall surface, and thus thermal denaturation easily occurs. This tendency becomes very high particularly in the case of handling a liquid with a high viscosity such as a prepolymer or a polymer, as in the case of use as a polymerizer or a purification and / or recovery device for a polymer. In such a case, a polymer adhering to the inner wall surface of the evaporation zone 5 easily undergoes coloring, high-molecular-weightization, and gelation, and when such denatured products are mixed, the polymer as a product is not preferable. Thus, the distance K (cm) of the guide 4 closest to the inner wall surface is more preferable the longer, but in the case of an industrial device, it is preferable to be short from the viewpoint of manufacturing cost and the viewpoint of obtaining a high evaporation capacity using a device as small as possible.

[0316] One of the features of the manufacturing device for the aromatic branched polycarbonate of the present embodiment is that a range (the above formula (IX)) of K (cm) that does not adversely affect the product and is as short as possible has been found.

[0317] More preferable is a range of 10 < K < 40, and a further more preferable range is 12 < K < 30.

[0318] In the manufacturing device for the aromatic branched polycarbonate of the present embodiment, the shape of the inner cross section of the horizontal surface of the side shell 10 of the evaporation zone 5 of the polymerization device contacted by the guide can be any shape such as a polygon, an ellipse, a circle, or the like.

[0319] The evaporation zone 5 is usually operated under reduced pressure, and thus can be any shape as long as it can withstand operation under reduced pressure, and is preferably a circular or approximately circular shape. Thus, the side shell 10 of the evaporation zone 5 is preferably a cylindrical shape. In this case, it is preferable to provide a conical bottom shell 11 at the lower portion of the cylindrical side shell 10, and to provide a cylindrical liquid discharge port 7 at the lowermost portion of the above bottom shell 11.

[0320] In the guide-contacting flow-down polymerization device for producing the aromatic branched polycarbonate according to the present embodiment, the side shell 10 and the bottom shell 11 of the evaporation zone 5 are formed of the above-mentioned cylindrical portion and conical portion, respectively, and in the case where the liquid or polymer liquid discharge port 7 after concentration is cylindrical, when the inner diameter of the cylindrical portion of the side shell 10 is set to D (cm), the length of the cylindrical portion of the side shell 10 is set to L (cm), and the inner diameter of the liquid discharge port 7 is set to d (cm), D, L, and d preferably satisfy the following formulas (X), (XI), (XII), and (XIII).

[0321] 100 ≤ D ≤ 1800 Formula (X)

[0322] 5 ≤ D / d ≤ 50 Formula (XI)

[0323] 0.5 ≤ L / D ≤ 30 Formula (XII)

[0324] h-20 ≤ L ≤ h+300 Formula (XIII)

[0325] Note that h (cm) is the length of the guide 4 shown in the above-mentioned <Condition (6)>.

[0326] In the above-mentioned guide-contacting flow-down polymerization device, a more preferable range of D (cm) is 150 ≤ D ≤ 1500, and further preferably 200 ≤ D ≤ 1200.

[0327] In addition, a more preferable range of D / d is 6 ≤ D / d ≤ 45, and further preferably 7 ≤ D / d ≤ 40.

[0328] In addition, a more preferable range of L / D is 0.6 ≤ L / D ≤ 25, and further preferably 0.7 ≤ L / D ≤ 20.

[0329] In addition, a more preferable range of L (cm) is h-10 ≤ L ≤ h+250, and further preferably h ≤ L ≤ h+200.

[0330] Note that as for D, d, and L, the balance of the amount of prepolymer that can be attached to the guide and the inner diameter (D) of the cylindrical portion of the side shell 10 and the size of the inner diameter d of the liquid discharge port 7 fall within the above-mentioned ranges.

[0331] The amount of prepolymer supplied is determined by the number of guides and the inner diameter (D) of the cylindrical portion of the side shell 10, and in order to draw out the fallen polymer (the viscosity of which is higher than that of the supplied prepolymer because polymerization has been performed), the inner diameter of the liquid discharge port 7, i.e., the pipe diameter (d), corresponding to the viscosity is required.

[0332] On the other hand, the liquid or melt is continuously supplied to the guide 4 from the upper portion, and therefore, by satisfying the above relation, the liquid having substantially the same viscosity or the melt having substantially the same melt viscosity with further increased polymerization degree continuously falls from the lower end of the guide 4 to the bottom housing 11. That is, the liquid having substantially the same viscosity or the polymer having substantially the same polymerization degree generated while flowing down along the guide 4 is retained in the lower portion of the bottom housing 11, thereby continuously producing the concentrated liquid having no variation in evaporation degree or the polymer having no variation in molecular weight. This is one of the other excellent features possessed by the guide-contacted flow-down type polymerization device which constitutes the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment.

[0333] The concentrated liquid or polymer retained in the lower portion of the bottom housing 11 is continuously drawn out via the liquid discharge port 7 by the discharge pump 8, and in the case of the polymer, is usually continuously pelletized by an extruder or the like. In this case, an additive or the like can also be added in the extruder.

[0334] Further, in the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment, it is preferable that the volume of the space in which the liquid can exist in the liquid supply zone 3 from the liquid receiving port 1 (the joint portion of the liquid receiving port 1 and the upper inner wall of the liquid supply zone 3) to the upper surface of the porous plate 2, V (m 3 ), and the upper area of the porous plate 2 including the area of the holes, T (m 2 ), satisfy the following equation (XIV).

[0335] 0.02 (m) ≤ V / T ≤ 0.5 (m) Equation (XIV)

[0336] The above volume of the space, V (m 3 ), is the volume of the liquid in the liquid supply zone 3 during the continuous operation of the guide-contacted flow-down type polymerization device, excluding the volume of the flow path control member 20.

[0337] The liquid retention amount in the liquid supply zone 3 is V (m 3 ), and in the case of a small amount, the residence time in the liquid supply zone 3 is small, thereby having no adverse effect due to thermal denaturation, and in order to obtain the concentrated liquid and / or polymer having a concentration degree or a polymerization degree of 1 ton / hour or more after the evaporation treatment and stably over a long period of time, it is preferable that the liquid be supplied as uniformly as possible to the holes of the porous plate 2. For this reason, the value of V / T is preferably within the range of the above equation (XIV). More preferably, the range of the value of V / T is 0.05 (m) ≤ V / T ≤ 0.4 (m), and further preferably, 0.1 (m) ≤ V / T ≤ 0.3 (m).

[0338] Further, in the flow-down type polymerization apparatus in which the guide of the apparatus for producing an aromatic branched polycarbonate according to the present embodiment contacts the liquid, it is preferable that the volume of the space V (m 3 ) in which the liquid can exist in the above-mentioned liquid supply zone 3 and the volume of the space Y (m 3 ) of the evaporation zone 5 satisfy the following equation.

[0339] 10≤ Y / V ≤ 500

[0340] In order to stably and efficiently perform the evaporation treatment of a large amount of liquid per unit time without causing a decrease in properties due to thermal denaturation, it is preferable that the value of Y / V be within this range. More preferably, the range of the value of Y / V is 15≤ Y / V ≤ 400, and further preferably 20≤ Y / V ≤ 300.

[0341] Note that the volume Y (m 3 ) of the space of the evaporation zone 5 means the volume of the space from the lower surface of the perforated plate 2 to the liquid discharge port 7, including the volume occupied by the guide 4.

[0342] In the flow-down type polymerization apparatus in which the guide of the apparatus for producing an aromatic branched polycarbonate according to the present embodiment contacts the liquid, in the case where one guide 4 is a cylindrical guide having an outer diameter r (cm) or a tubular guide in which the liquid and / or the gaseous substance or the molten prepolymer does not enter the inside of the guide, it is preferable that the outer diameter r (cm) satisfy the following equation (XV).

[0343] 0.1≤ r≤ 1 Equation (XV)

[0344] The guide 4 performs the evaporation concentration or the polymerization reaction while flowing the liquid or the molten prepolymer, and also has a function of retaining the liquid or the molten prepolymer for a certain period of time. This retention time is related to the evaporation time or the polymerization reaction time, and the liquid viscosity or the molten viscosity thereof gradually increases as the evaporation or the polymerization proceeds, and thus the retention time and the retention amount thereof gradually increase. With respect to the amount of the liquid or the molten prepolymer retained by the guide 4, even if the molten viscosity is the same, it differs depending on the outer surface area of the guide 4, that is, the outer diameter thereof in the case of a cylindrical guide or a tubular guide.

[0345] In addition, the guide 4 provided in the flow-down type polymerization apparatus needs to have a strength that supports the mass of the liquid or the molten prepolymer or the polymer retained in addition to the mass of the guide 4 itself. In this sense, the thickness of the guide 4 is important, and in the case of a cylindrical guide or a tubular guide, it is preferable that the above equation (XV) be satisfied.

[0346] When the outer diameter r (cm) of the guide 4 is 0.1 or more, stable operation for a long time can be achieved in terms of strength. In addition, by making r (cm) 1 or less, it is possible to prevent the guide itself from becoming too heavy, for example, to avoid undesirable situations such as having to make the thickness of the porous plate 2 extremely thick in order to hold the guide in contact with the flow-down type polymerization device, to prevent an increase in the amount of liquid or raw material molten prepolymer or polymer held from becoming excessive, to avoid undesirable situations such as a large variation in concentration or a large variation in molecular weight.

[0347] More preferably, the outer diameter r (cm) of the guide 4 is in the range of 0.15 ≤ r ≤ 0.8, and further preferably in the range of 0.2 ≤ r ≤ 0.6.

[0348] There is no particular limitation on the positional relationship between the guide 4 and the porous plate 2, and the positional relationship between the guide 4 and the holes of the porous plate 2, as long as the liquid or raw material molten prepolymer or polymer can flow down in contact with the guide.

[0349] The guide 4 and the porous plate 2 can be in contact with each other, or can not be in contact with each other.

[0350] It is preferable to arrange the guide 4 in a manner corresponding to the holes of the porous plate 2, but it is not limited thereto. The reason for this is because it is sufficient if the liquid or raw material molten prepolymer or polymer falling from the porous plate 2 comes into contact with the guide 4 at an appropriate position.

[0351] As a preferable method of arranging the guide 4 in a manner corresponding to the holes of the porous plate 2, for example, the following can be cited: (1) a method of arranging the guide 4 in a state in which the upper end of the guide 4 is fixed to the lower surface of the flow path control member 20 or the like, and the guide 4 penetrates the vicinity of the center of the holes of the porous plate 2; (2) a method of arranging the guide 4 in a state in which the upper end of the guide 4 is fixed to the peripheral portion of the upper end of the holes of the porous plate 2, and the guide 4 penetrates the holes of the porous plate 2; (3) a method of arranging the guide 4 in a state in which the upper end of the guide 4 is fixed to the lower surface of the porous plate 2, and the guide 4 does not penetrate the holes of the porous plate 2; and the like.

[0352] As a method of causing the liquid or raw material molten prepolymer or polymer to flow down along the guide 4 through the porous plate 2, a method of causing it to flow down by hydraulic head or self weight, or a method of extruding the liquid or raw material molten prepolymer or polymer from the porous plate 2 by pressurization using a pump or the like can be cited. A preferable method is a method of supplying a predetermined amount of liquid or raw material molten prepolymer or polymer to the liquid supply area 3 under pressure using a supply pump, and causing the liquid or raw material molten prepolymer or polymer introduced into the guide 4 through the porous plate 2 to flow down along the guide 4 by self weight.

[0353] In the apparatus for producing an aromatic branched polycarbonate of the present embodiment, a preferable material of such a guide 4 can be selected from, for example, metals such as stainless steel, carbon steel, hastelloy, nickel, titanium, chromium, aluminum, and other alloys, and high-heat-resistant polymer materials, and the like. A particularly preferable material is stainless steel.

[0354] In addition, the surface of the guide 4 can be subjected to various treatments as needed, such as plating, lining, passivation treatment, pickling, cleaning with a solvent or phenol, and the like.

[0355] The reason why the apparatus for producing an aromatic branched polycarbonate of the present embodiment can produce a high-quality and high-performance concentrated liquid or polymer with little coloring, good color tone, and excellent mechanical properties at a fast evaporation rate or a fast polymerization rate, stably over a long period of time (without variation in molecular weight or the like in the case of producing a polymer) on an industrial scale is considered as follows.

[0356] That is, in the flow-down type polymerization apparatus in which the guide contacts the flow of the raw material liquid, the raw material liquid is introduced from the liquid receiving port 1 to the guide 4 via the liquid supply zone 3 and the porous plate 2, and is concentrated or the degree of polymerization is increased while flowing down along the guide 4. In this case, effective internal stirring and surface renewal are performed while the liquid or the molten prepolymer flows down along the guide 4, and the extraction of low-boiling substances is effectively performed, so that the concentration or polymerization is performed at a fast rate. As the concentration or polymerization proceeds, the viscosity becomes high, so the adhesion to the guide 4 increases, and the amount of the liquid or the melt adhering to the guide 4 increases as it goes to the lower part of the guide 4. This means that the residence time of the liquid or the molten prepolymer on the guide, that is, the evaporation time or the polymerization reaction time increases. Also, the surface area per unit weight of the liquid or the molten prepolymer flowing down by the self-weight while being supported by the guide 4 is very large, and the surface renewal is effectively performed, so that the evaporation concentration or the polymerization of the high-molecular-weight portion in the latter half can be easily achieved in a high-viscosity region, which is impossible with the evaporation apparatus or the mechanically stirred polymerizer known in the past. This is one of the excellent features of the apparatus for producing an aromatic branched polycarbonate of the present embodiment.

[0357] In the guide-contacted flow-down type polymerization apparatus that constitutes the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment, the amount of the liquid or melt adhering to the guide 4 increases in the latter half of the evaporation or polymerization, but since only the adhesion holding force that corresponds to the viscosity thereof is maintained, substantially the same amount of the liquid or melt having substantially the same viscosity at the same height of the plurality of guides 4 is supported by each guide 4. On the other hand, the liquid or melt is continuously supplied from the upper portion to the guide 4, and therefore, the liquid having substantially the same viscosity or the melt having substantially the same melt viscosity with the degree of polymerization further increased continuously falls from the lower end of the guide 4 to the bottom housing 11. That is, the liquid having substantially the same viscosity or the polymer having substantially the same degree of polymerization that is generated while flowing down along the guide 4 is retained in the lower portion of the bottom housing 11, and therefore, the concentrated liquid without variation in the degree of evaporation or the polymer without variation in the molecular weight is continuously manufactured. This is one of the excellent features of the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment. The concentrated liquid or the polymer retained in the lower portion of the bottom housing 11 is continuously extracted via the liquid discharge port 7 by the discharge pump 8, and in the case of the polymer, is usually continuously pelletized by an extruder or the like. In this case, an additive or the like can also be added in the extruder.

[0358] The perforated plate 2 that constitutes the guide-contacted flow-down type polymerization apparatus is usually selected from a flat plate, a corrugated plate, a plate in which the center portion is thickened, and the like. As for the shape of the cross section of the perforated plate 2, a circular shape, an elliptical shape, a triangular shape, a polygonal shape, and the like are usually selected.

[0359] The cross section of the hole of the perforated plate is usually selected from a circular shape, an elliptical shape, a triangular shape, a slit shape, a polygonal shape, a star shape, and the like.

[0360] The cross-sectional area of the hole is usually in the range of 0.01 cm 2 ~ 100 cm 2 , preferably 0.05 cm 2 ~ 10 cm 2 , and more preferably in the range of 0.1 cm 2 ~ 5 cm 2 . The spacing between the holes is usually in the range of 1 mm ~ 500 mm, preferably 10 mm ~ 100 mm, in terms of the distance between the centers of the holes. The holes of the perforated plate 2 can be holes that penetrate the perforated plate 2, or can be in a state in which the guides 4 are installed without penetrating the perforated plate 2. In addition, it can be tapered in the depth direction.

[0361] In the guide-contacted flow-down type polymerization apparatus described above, as for the perforated plate 2 and the holes thereof, it is preferable to satisfy Formula (VI), Formula (VII), as described above.

[0362] In addition, the guide 4 that constitutes the guide-contacted flow-down type polymerization apparatus is preferably not provided with a heating source such as a heating medium or an electric heater inside itself, and is preferably made of a material having a ratio of the length of the vertical cross section to the average length of the outer periphery of the horizontal cross section that is very large. The ratio of (the length of the vertical cross section / the average length of the outer periphery of the horizontal cross section) is usually in the range of 10 to 1,000,000, and preferably in the range of 50 to 100,000.

[0363] The shape of the horizontal cross section of the guide 4 is usually selected from a circular shape, an elliptical shape, a triangular shape, a quadrangular shape, a polygonal shape, a star shape, and the like. The shape of the cross section of the guide 4 can be the same or different in the length direction. In addition, the guide 4 can be hollow. The guide 4 of the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment does not have a heating source inside itself, and thus does not have a problem of thermal denaturation of the liquid on the surface of the guide 4, which is an important feature.

[0364] The guide 4 can be a single guide such as a wire-shaped guide, a thin rod-shaped guide, a thin tube-shaped guide that does not allow the liquid or the molten prepolymer to enter the inside, and the like, or can be a guide obtained by combining a plurality of guides by twisting or the like. In addition, the guide can be a mesh-shaped guide or a punched plate-shaped guide.

[0365] The surface of the guide 4 can be smooth, can have a concave-convex shape, or can have a protrusion or the like in a partial region. The guide 4 is preferably a cylindrical guide such as a wire-shaped guide or a thin rod-shaped guide, the above-described thin tube-shaped guide, a mesh-shaped guide, or a punched plate-shaped guide.

[0366] In the guide-contacted flow-down type polymerization apparatus that constitutes the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment that can produce a high-quality concentrated liquid or a polymer on an industrial scale (production amount, long-term stable production, and the like), it is particularly preferable to use a guide in which a plurality of wire-shaped guides or thin rod-shaped guides or the above-described thin tube-shaped guides are combined with a support material in the lateral direction at appropriate intervals in the vertical direction.

[0367] For example, a lattice-shaped or mesh-shaped guide obtained by fixing a plurality of wire-shaped guides or thin rod-shaped guides or the above-described thin tube-shaped guides with a support material in the lateral direction at appropriate intervals, for example, at intervals of 1 cm to 200 cm; a three-dimensional guide obtained by arranging a plurality of lattice-shaped or mesh-shaped guides in the front and back and combining the guides with a support material in the lateral direction at appropriate intervals, for example, at intervals of 1 cm to 200 cm; or a three-dimensional guide in the shape of a climbing frame obtained by fixing a plurality of wire-shaped guides or thin rod-shaped guides or the above-described thin tube-shaped guides in the front and back and left and right with a support material in the lateral direction at appropriate intervals, for example, at intervals of 1 cm to 200 cm.

[0368] The lateral support material not only helps maintain the same spacing between the guides, but also helps increase the strength of the guides, which can be planar or curved, or three-dimensional. The support material can be the same material as the guides, or a different material.

[0369] The guide-contacting flow-down polymerization device of the apparatus for producing the aromatic branched polycarbonate of the present embodiment is a device that evaporates the low-boiling-point substance from the above-mentioned liquid containing a substance having a lower boiling point than the liquid.

[0370] The above-mentioned liquid can be at room temperature, but is usually supplied from the liquid receiving port 1 to the guide-contacting flow-down polymerization device in a heated state. In addition, a jacket or the like is preferably provided on the outer wall surface of the guide-contacting flow-down polymerization device, and heating by steam or a heat medium or the like is preferably performed in the jacket as needed, whereby heating and / or temperature retention of the liquid supply area 3, the flow path control member 20, or the porous plate 2, and temperature retention of the evaporation area 5 or the porous plate 2, and the like are performed.

[0371] The guide-contacting flow-down polymerization device of the present embodiment is not only used as a device for simply concentrating the liquid, but can also be used as an evaporation device that targets a liquid having a high viscosity, such as a polymerization device for condensation-type polymers, a purification device for thermoplastic polymers containing monomers or oligomers or by-products or the like as low-boiling-point substances, a separation and recovery device for separating and recovering the polymers from a solution of the thermoplastic polymers. Thus, the guide-contacting flow-down polymerization device of the present embodiment can be used as a polymerization device for condensation-type polymers in which the liquid supplied from the above-mentioned liquid supply area 3 is a monomer, a mixture of two or more monomers, a prepolymer of a condensation-type polymer, a molten liquid of a condensation-type polymer, the low-boiling-point substance is a by-product and / or an oligomer generated by a condensation reaction, and the prepolymer of the condensation-type polymer and / or the polymerization degree of the above-mentioned polymer is increased by evaporating and removing the low-boiling-point substance from the above-mentioned molten liquid.

[0372] As the above-mentioned condensation-type polymers, polycarbonates such as aliphatic polycarbonates or aromatic polycarbonates and various copolymerized polycarbonates, and the like; polyester polycarbonates, and the like are preferable.

[0373] By using the apparatus for producing an aromatic branched polycarbonate having the above-mentioned guide-contacting flow-down polymerization device, a condensation-type polymer that is not colored or contains gel-like substances or solid foreign matter, does not have a variation in molecular weight, and is high in purity and performance can be produced stably over a long period of time.

[0374] The guide-contacting flow-down polymerization device of the apparatus for producing the aromatic branched polycarbonate of the present embodiment is suitable for evaporating and removing a low-boiling-point substance from a liquid having a high viscosity.

[0375] For example, in the case where the flow-down type polymerization device using the guide member of the present embodiment is used as a polymerizer of a condensation type polymer, in the conventionally known polymerizer, there are sites where a portion of the liquid remains in a state of being heated for a long time, and thus the remaining liquid is denatured by coloring, gelation, crosslinking, ultrahigh molecular weight, solidification, scorching, carbonization, and the like, and it is not possible to avoid the shortcoming that these denatured products are slowly or concentratedly mixed into the polymer, but the flow-down type polymerization device of the manufacturing device for the aromatic branched polycarbonate of the present embodiment not only does not have such a shortcoming, but also has a superior effect that the conventional polymerizer does not have.

[0376] That is, for example, in the case of manufacturing the aromatic branched polycarbonate by polymerizing the molten prepolymer obtained from the aromatic dihydroxy compound and the diaryl carbonate, the temperature of the reaction generally needs to be in the range of 200°C to 350°C, and in particular, in the latter half of the polymerization, the viscosity thereof sharply increases, and thus it is necessary to draw the aromatic monohydroxy compound generated in the equilibrium reaction from the ultrahigh viscosity material, and thus, in the case of using the polymerizer such as the horizontal double shaft stirring type reactor for the ultrahigh viscosity polymer up to now, it is necessary to react for a long time at a high temperature of 300°C or higher and under a high vacuum of 133 Pa or lower, and it is difficult to manufacture the high molecular weight body for a sheet or the like.

[0377] However, in the flow-down type polymerization device of the manufacturing device for the aromatic branched polycarbonate of the present embodiment, the effective surface renewal accompanied by the internal stirring is performed, and thus it is possible to perform the polymerization reaction at a lower temperature. Thus, the preferable reaction temperature is 100°C to 290°C, and further preferably 150°C to 270°C. In comparison with the case of the conventional mechanical stirring type polymerizer, it is possible to sufficiently perform the polymerization at a lower temperature, which is a feature of the manufacturing device for the aromatic branched polycarbonate of the present embodiment, and this is also one reason why it is possible to manufacture the high quality aromatic branched polycarbonate without coloring or a decrease in physical properties.

[0378] Further, in the conventionally known polymerizer, there are shortcomings such as the leakage of air or the like from the sealing portion of the stirrer under a high vacuum, the mixing of foreign matter, and the like, but in the flow-down type polymerization device of the manufacturing device for the aromatic branched polycarbonate of the present embodiment, there is no mechanical stirring, and there is no sealing portion of the stirrer, and thus the leakage of air or the like or the mixing of foreign matter is very small, and it is possible to manufacture the aromatic branched polycarbonate of high purity and high performance.

[0379] It should be noted that in the case where a condensation type polymer is produced using the apparatus for producing an aromatic branched polycarbonate of the present embodiment, as the polymerization reaction proceeds, low-boiling-point substances generated as by-products by the equilibrium reaction are removed from the reaction system, thereby increasing the reaction rate. Therefore, it is preferable to use a method in which a non-reactive gas such as nitrogen, argon, helium, carbon dioxide, or a lower hydrocarbon gas, which does not adversely affect the reaction, is introduced into the flow-by-contact type polymerization apparatus, and the low-boiling-point substances are removed together with these gases; a method in which the reaction is performed under reduced pressure; or the like. Alternatively, it is also preferable to use a method in which the above-described methods are used in combination, in which case it is not necessary to introduce a large amount of non-reactive gas into the flow-by-contact type polymerization apparatus, but it is sufficient to maintain the inside of the apparatus in an atmosphere of non-reactive gas to a certain extent.

[0380] In addition, the reaction pressure in the flow-by-contact type polymerization apparatus in the case where a condensation type polymer is produced using the apparatus for producing an aromatic branched polycarbonate of the present embodiment differs depending on the kind of low-boiling-point substances generated as by-products, or the kind or molecular weight of the polymer to be produced, the polymerization temperature, or the like, and for example, in the case where an aromatic branched polycarbonate is produced from a molten prepolymer obtained using bisphenol A and diphenyl carbonate, in the case where the number average molecular weight of the polymer is in the range of 5,000 or less, the reaction pressure is preferably in the range of 400 PaA to 3,000 PaA, and in the case where the number average molecular weight is in the range of 5,000 to 10,000, the reaction pressure is preferably in the range of 50 PaA to 500 PaA. In the case where the number average molecular weight is 10,000 or more, the reaction pressure is preferably 300 PaA or less, and particularly preferably in the range of 20 PaA to 250 PaA.

[0381] In the case where a condensation type polymer is produced using the flow-by-contact type polymerization apparatus constituting the apparatus for producing an aromatic branched polycarbonate of the present embodiment as a polymerizer, it is possible to produce a polymer having a target degree of polymerization using only one such flow-by-contact type polymerization apparatus, but it is also possible to adopt a method in which two or more flow-by-contact type polymerization apparatuses are connected to sequentially increase the degree of polymerization, depending on the degree of polymerization of the molten monomer or molten prepolymer used as a raw material, the production amount of the polymer, or the like.

[0382] In this case, two or more flow-by-contact type polymerization apparatuses are preferably connected by any one of series connection, parallel connection, and a combination of series connection and parallel connection.

[0383] In addition, in this case, in each flow-by-contact type polymerization apparatus, it is possible to adopt a guide and reaction conditions that are suitable for the degree of polymerization of the prepolymer or polymer to be produced.

[0384] For example, in the case of using a first guide-contacted flow-down polymerization device, a second guide-contacted flow-down polymerization device, a third guide-contacted flow-down polymerization device, a fourth guide-contacted flow-down polymerization device, and the like in this order to increase the polymerization degree, if the total external surface area of the guide of each polymerization device is set to S1, S2, S3, S4, and the like, it is possible to set S1≥S2≥S3≥S4≥...

[0385] In addition, the polymerization temperature can be the same in each polymerization device, or can be increased in order.

[0386] The polymerization pressure can be decreased in order in each polymerization device.

[0387] In this sense, for example, in the case of using a first guide-contacted flow-down polymerization device and a second guide-contacted flow-down polymerization device in this order to increase the polymerization degree, it is preferable to use a guide in which the total external surface area S1 (m 2 ) of the guide of the first polymerization device and the total external surface area S2 (m 2 ) of the guide of the second polymerization device satisfy the following formula (XVI):

[0388] 1≤S1 / S2≤20 Formula (XVI)

[0389] By setting S1 / S2 to be 1 or more, it is possible to suppress the variation in the molecular weight, to achieve long-term stable production, and to obtain the desired production amount.

[0390] By setting S1 / S2 to be 20 or less, it is possible to suppress the flow rate of the molten prepolymer flowing down along the guide in the second polymerization device, and as a result, it is possible to sufficiently secure the residence time of the molten prepolymer, and to obtain a polymer having the desired molecular weight. A more preferable range is 1.5≤S1 / S2≤15.

[0391] In the production device for the aromatic branched polycarbonate of the present embodiment, it is preferable to further provide a non-active gas absorption device for absorbing non-active gas in the molten prepolymer of the condensation-type polymer before being supplied to the guide-contacted flow-down polymerization device.

[0392] In addition, in the case of using a plurality of guide-contacted flow-down polymerization devices, it is preferable to provide a non-active gas absorption device for absorbing non-active gas in the molten prepolymer before being supplied to each guide-contacted flow-down polymerization device. By providing the non-active gas absorption device, it is possible to further improve the effects of the present application.

[0393] Hereinafter, a case in which one guide-contacted flow-down polymerization device and one non-active gas absorption device are used in a pair will be described.

[0394] The molten prepolymer is introduced into a non-active gas absorbing device before being supplied to the guide contact flow type polymerization device. In the non-active gas absorbing device, the molten prepolymer is treated with a non-active gas so that the molten prepolymer absorbs the non-active gas, whereby the molten prepolymer absorbs a specific amount of non-active gas of 0.0001 NL to 1 NL per 1 kg of the molten prepolymer (where NL is the volume measured under standard temperature / pressure conditions), and then the molten prepolymer absorbing the specific amount of non-active gas is supplied to the guide contact flow type polymerization device and polymerized.

[0395] The treatment of the molten prepolymer with a non-active gas means that the molten prepolymer absorbs the non-active gas under conditions in which the molten prepolymer is not likely to polymerize.

[0396] The amount of non-active gas absorbed by the molten prepolymer is preferably 0.0001 NL to 1 NL, more preferably in the range of 0.001 NL to 0.8 NL, and further preferably in the range of 0.005 NL to 0.6 NL, per 1 kg of the molten prepolymer.

[0397] In the case where the amount of absorbed non-active gas is less than 0.0001 NL per 1 kg of the molten prepolymer, the effect of increasing the polymerization rate by using a prepolymer absorbing an active gas and the effect of stably producing an aromatic branched polycarbonate by using a prepolymer absorbing a non-active gas become small. In addition, there is no need to make the amount of non-active gas absorbed by the molten prepolymer more than 1 NL per 1 kg of the molten prepolymer.

[0398] By polymerizing the molten prepolymer absorbing the non-active gas in the range of the above numerical values in the guide contact flow type polymerization device constituting the production device of the aromatic branched polycarbonate of the present embodiment, the effects of the present application can be further improved.

[0399] The amount of inert gas absorbed by the molten prepolymer can usually be easily measured by directly measuring the amount of inert gas supplied. In an inert gas absorption device, where inert gas is absorbed by the molten prepolymer while it is flowing through, the amount of absorbed inert gas can be determined from the difference between the amount of inert gas supplied and the amount of inert gas discharged. Alternatively, a predetermined amount of molten prepolymer can be supplied to an inert gas absorption device containing inert gas at a predetermined pressure, and the amount of absorbed inert gas can be measured based on the pressure decrease of the absorption device caused by the absorption of inert gas by the molten prepolymer. Furthermore, the amount of absorbed inert gas can be measured in batches by supplying a predetermined amount of molten prepolymer to the inert gas absorption device and then measuring the amount of inert gas absorbed; or it can be measured continuously by continuously supplying the molten prepolymer to the inert gas absorption device and continuously extracting it while simultaneously measuring the amount of inert gas absorbed.

[0400] In this embodiment, an inactive gas absorption device is used to treat the molten prepolymer with an inactive gas under a specified pressure and under conditions where the molten prepolymer is not prone to polymerization, thereby causing the molten prepolymer to absorb the inactive gas.

[0401] To allow a molten prepolymer to absorb inactive gases means to disperse and / or dissolve the inactive gases in the molten prepolymer.

[0402] Dispersion refers to the state in which inactive gases are mixed in the molten prepolymer as bubbles, forming a gas-liquid mixed phase. Dissolution refers to the state in which inactive gases are mixed in the molten prepolymer, forming a uniform liquid phase.

[0403] In particular, the inactive gas is not only dispersed in the molten prepolymer but also dissolved in the molten prepolymer.

[0404] In order to efficiently dissolve inert gases in molten prepolymers, it is preferable to increase the gas-liquid interface area to achieve good contact efficiency and to absorb inert gases under pressure.

[0405] As the non-active gas absorbing device that constitutes the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment, there is no particular limitation as long as it is a device that can absorb non-active gas into the molten prepolymer. For example, there can be cited the packed column type absorbing device, the tray type absorbing device, the spray tower type absorbing device, the fluidized packed column type absorbing device, the liquid membrane cross flow absorbing type absorbing device, the high speed cyclone type absorbing device, the mechanical force utilizing type absorbing device, and the like, which are well known devices, the device that absorbs while the molten prepolymer is falling along the guide under a non-active gas atmosphere, and the like, which are described in Chemical Plant Design & Operation Series No. 2, Revised Edition, Gas Absorption, pp. 49-54 (March 15, 1956, published by the Chemical Industry Co., Ltd.).

[0406] In addition, it can also be a device that directly supplies non-active gas and absorbs it in the pipe that supplies the molten prepolymer to the guide contact falling type polymerization apparatus. It is particularly preferable to use the spray tower type absorbing device, the device that absorbs while falling along the guide.

[0407] As the non-active gas absorbing device, it is particularly preferable to use the same type of device as the guide contact falling type polymerization apparatus.

[0408] The non-active gas absorbing device operates under conditions in which polymerization hardly proceeds, and thus is completely different in function from the guide contact falling type polymerization apparatus. The excellent feature of this type of device is that the surface area per unit mass of the molten substance during the falling along the guide is very large, and the surface renewal of the molten substance and the internal agitation are very good, and these two are combined with each other, and thus very effective non-active gas absorption can be achieved in a short time.

[0409] Unlike the guide contact falling type polymerization apparatus, in the non-active gas absorbing device, the viscosity of the molten prepolymer in the upper portion and the lower portion of the guide hardly changes, and thus the processing capacity per unit time of the molten prepolymer is large. Therefore, even if it is the same type, the non-active gas absorbing device can generally be further downsized compared to the guide contact falling type polymerization apparatus.

[0410] The manufacturing method of the aromatic branched polycarbonate that is preferable in the present embodiment will be described.

[0411] When the number average molecular weight of the molten prepolymer before and after the absorption of non-active gas is set to Ml, M2, respectively, the change in the molecular weight (M2-Ml) before and after the absorption of non-active gas is substantially preferably 2,000 or less, more preferably 1,000 or less, and further more preferably 500 or less.

[0412] The temperature at which the molten prepolymer absorbs the non-reactive gas is not particularly limited as long as it is in a molten state, and is usually in the range of 150°C to 350°C, preferably in the range of 180°C to 300°C, and more preferably in the range of 230°C to 270°C.

[0413] The pressure Pg (PaA) at which the molten prepolymer absorbs the non-reactive gas is preferably higher than the pressure at which the molten prepolymer is produced.

[0414] That is, it is preferable to absorb the non-reactive gas under the same pressure as the reaction pressure used when producing the molten prepolymer of the aromatic branched polycarbonate by reacting the aromatic dihydroxy compound with the diaryl carbonate, or under a higher pressure than that.

[0415] In addition, Pg (PaA) is a pressure higher than the pressure Pp (PaA) at which the subsequent guide contacts the polymerization reaction in the polymerization device, and it is preferable to satisfy the following relationship with respect to Ml (the number average molecular weight of the molten prepolymer before absorbing the non-reactive gas).

[0416] Formula: Pg > 4 x 10 12 Ml -2.6871

[0417] In the case where the pressure Pg (PaA) at which the molten prepolymer absorbs the non-reactive gas does not satisfy the above relationship, the effect of increasing the polymerization rate achieved by using the prepolymer that has absorbed the non-reactive gas and the effect of stably producing the aromatic branched polycarbonate achieved by using the prepolymer that has absorbed the non-reactive gas become small.

[0418] From the viewpoint of improving the absorption rate of the non-reactive gas in the molten prepolymer, and as a result, being able to reduce the non-reactive gas absorption device, it is particularly preferable that the pressure at the time of absorbing the non-reactive gas be normal pressure or pressurized.

[0419] The upper limit of the pressure at the time of absorbing the non-reactive gas is not particularly limited, and is usually 2 x 10 7 PaA or less, preferably 1 x 10 7 PaA or less, and more preferably 5 x 10 6 PaA or less.

[0420] As the method of causing the molten prepolymer to absorb the non-reactive gas in the non-reactive gas absorption device, it can be a method of absorbing a large portion of the non-reactive gas supplied to the non-reactive gas absorption device in the molten prepolymer, or a method of absorbing a portion of the supplied non-reactive gas in the molten prepolymer.

[0421] As the former method, for example, there can be mentioned: a method of using a spray tower type absorption device or a device for absorbing an inert gas while causing the molten prepolymer to fall along the guide, supplying an inert gas in an amount substantially equivalent to the target amount of the inert gas to be absorbed in the molten prepolymer, and absorbing the inert gas while keeping the pressure of the device substantially constant; a method of using a device for directly supplying an inert gas to a pipe through which the molten prepolymer is supplied to the guide contact flow type polymerization device; and the like.

[0422] In addition, as the latter method, for example, there can be mentioned: a method of using a spray tower type absorption device or a device for absorbing an inert gas while causing the molten prepolymer to fall along the guide as an inert gas absorption device, causing an inert gas in an amount exceeding the amount to be absorbed in the molten prepolymer to flow in the inert gas absorption device, and discharging the excess inert gas from the inert gas absorption device; and the like.

[0423] The former method is particularly preferable from the viewpoint of further reducing the amount of use of the inert gas.

[0424] In addition, the inert gas absorption can be either of a continuous method in which the molten prepolymer is continuously supplied to the inert gas absorption device and caused to absorb the inert gas, and the molten prepolymer having absorbed the inert gas is continuously withdrawn, and a batch method in which the molten prepolymer is batchwise charged to the absorption device and caused to absorb the inert gas.

[0425] The inert gas refers to a collective term of a gas which does not chemically react with the molten prepolymer and is stable under the polymerization conditions, and as the inert gas, for example, there can be mentioned nitrogen, argon, helium, carbon dioxide, an organic compound which is in a gaseous state at a temperature at which the prepolymer is kept in a molten state, a lower hydrocarbon gas having 1 to 8 carbon atoms, and the like, and nitrogen is particularly preferable.

[0426] In the method for producing an aromatic branched polycarbonate according to the present embodiment, the pressure of the molten prepolymer having absorbed the inert gas in the supply pipe of the molten prepolymer between the inert gas absorption device and the guide contact flow type polymerization device is kept at a prescribed pressure in the guide contact flow type polymerization device, and therefore, it is preferable to provide a prescribed pressure regulating valve immediately before the inlet of the guide contact flow type polymerization device, thereby controlling the pressure of the molten prepolymer.

[0427] The guide contacts the inside of the falling film type polymerization apparatus at a higher vacuum, and the molten prepolymer near the supply port of the apparatus is easily sucked by the apparatus to become a state of low pressure. Therefore, sometimes the non-active gas absorbed in the non-active gas absorption apparatus separates and aggregates from the molten prepolymer. Therefore, in order to prevent these problems, it is preferable to supply the molten prepolymer to the guide contacting the falling film type polymerization apparatus in a manner to maintain the pressure of the molten prepolymer above the pressure at which the non-active gas is absorbed in the non-active gas absorption apparatus.

[0428] Specifically, it is preferable to be in the range of 15 kPaA to 200 kPaA, more preferably 20 kPaA to 150 kPaA, and further preferably 20 to 100 kPaA.

[0429] In the case where the pressure regulating valve is not provided, or in the case where the pressure is lower than the pressure at which the molten prepolymer absorbs the non-active gas, the pressure of the molten prepolymer in the pipe becomes unstable, the non-active gas such as nitrogen temporarily absorbed by the molten prepolymer separates or aggregates to become unstable in uniformity of the molten prepolymer, the uniform and continuous foaming phenomenon of the molten prepolymer in the guide contacting falling film type polymerization apparatus is hindered, a stable product cannot be manufactured, and reduction in color tone, fish eyes, gels, and the like are easily generated.

[0430] On the other hand, even if 200 kPaA is exceeded, the effect does not change, an excessive load is applied to the discharge gear pump and the pipe of the non-active gas absorption apparatus, and it is necessary to improve the pressure resistance, which is not realistic, and therefore, the upper limit value is preferably set to 200 kPaA.

[0431] The manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment can be any one as long as it satisfies the above various conditions and has a mechanical strength corresponding thereto, and can be additionally provided with any device / equipment having other functions required for continuous operation.

[0432] In addition, the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment can be an apparatus in which a plurality of the above guide contacting falling film type polymerization apparatuses or non-active gas absorption apparatuses are combined, and can be an apparatus additionally provided with a device / equipment having other functions than evaporation.

[0433] Further, from the same viewpoint as described above, in the case where the apparatus for producing an aromatic branched polycarbonate of the present embodiment has a further connected guide-contact flow-down polymerization apparatus in the guide-contact flow-down polymerization apparatus described above, and a non-active gas absorbing apparatus is provided in front of each of these guide-contact flow-down polymerization apparatuses, it is preferable that a pressure regulating valve is provided immediately in front of the inlet of each of the guide-contact flow-down polymerization apparatuses described above, and the pressure of the molten prepolymer to which the non-active gas is absorbed in the supply pipe from the non-active gas absorbing apparatus to each of the guide-contact flow-down polymerization apparatuses is maintained at 15 to 200 kPaA, and the supply is performed. More preferably, it is 20 to 150 kPaA, and further preferably, it is 20 to 100 kPaA.

[0434] In the apparatus for producing an aromatic branched polycarbonate of the present embodiment, the material of the guide-contact flow-down polymerization apparatus and the pipe is not particularly limited, and is usually selected from metals such as stainless steel, carbon steel, hastelloy, nickel, titanium, chromium, and other alloys, and high-heat-resistant polymer materials. Further, the surface of these materials can be subjected to various treatments such as plating, lining, passivation treatment, pickling, phenol cleaning, and the like as needed. Stainless steel or nickel, enamel, and the like are preferable, and stainless steel is particularly preferable.

[0435] Note that the discharge pump 8 for discharging the molten prepolymer or the aromatic branched polycarbonate from the discharge port 12 is usually preferably a gear pump type capable of quantitatively discharging a high-viscosity material, and the material of these gear pumps can be stainless steel or other special metals.

[0436] [Materials for producing an aromatic branched polycarbonate]

[0437] Hereinafter, the materials used when producing an aromatic branched polycarbonate using the apparatus for producing an aromatic branched polycarbonate of the present embodiment, that is, an aromatic dihydroxy compound and a diaryl carbonate, are described.

[0438] (Aromatic dihydroxy compound)

[0439] The aromatic dihydroxy compound used when producing an aromatic branched polycarbonate is a compound represented by the following formula.

[0440] HO-Ar-OH

[0441] (In the formula, Ar represents a divalent aromatic group.)

[0442] The divalent aromatic group Ar is defined in the same manner as the definition described above.

[0443] The aromatic dihydroxy compound used when the aromatic branched polycarbonate is produced using the apparatus for producing an aromatic branched polycarbonate of the present embodiment can be one kind alone or two or more kinds.

[0444] As the aromatic dihydroxy compound, bisphenol A is preferred, for example. In addition, a ternary aromatic trihydroxy compound for introducing a branched structure can also be used in combination.

[0445] As the bisphenol A, a high-purity product for polycarbonate having a chlorine content of 1 ppb or less is particularly preferred.

[0446] (diphenyl carbonate)

[0447] The diphenyl carbonate used when the aromatic branched polycarbonate is produced using the apparatus for producing an aromatic branched polycarbonate of the present embodiment is represented by the following formula.

[0448]

[0449] (In the above formula, Ar" is defined in the same manner as the above definition, and each is preferably a monovalent aromatic group having 5 to 20 carbon atoms.)

[0450] As the above diphenyl carbonate, a symmetric type diphenyl carbonate such as unsubstituted diphenyl carbonate, di(tolyl) carbonate, di(tert-butylphenyl) carbonate, and the like, lower alkyl-substituted diphenyl carbonates, and the like are preferred, and diphenyl carbonate, which is the simplest structure of the diphenyl carbonates, is particularly preferred. These diphenyl carbonates can be used alone as one kind or two or more kinds in combination.

[0451] The diphenyl carbonate used as a raw material for producing the aromatic branched polycarbonate is particularly preferably diphenyl carbonate produced by the following method.

[0452] First, ethylene carbonate produced by reacting ethylene oxide with CO2 and purified is obtained, and then dimethyl carbonate produced by reacting the ethylene carbonate with methanol and purified is obtained. The above dimethyl carbonate is reacted with purified phenol by a reaction distillation method to obtain diphenyl carbonate, and this is purified, whereby the target diphenyl carbonate is obtained. This is an ultrahigh-purity product not containing alkali metals, alkaline earth metals, and chlorine.

[0453] (melted prepolymer)

[0454] The molten prepolymer used in the case where the aromatic branched polycarbonate is manufactured using the manufacturing apparatus of the present embodiment is manufactured from the above-described aromatic dihydroxy compound and the diaryl carbonate, and the use ratio (charge ratio) thereof varies depending on the kind of the aromatic dihydroxy compound and the diaryl carbonate used, the polymerization temperature, and other polymerization conditions. The diaryl carbonate is generally used in a ratio of 0.9 to 2.5 moles, preferably 0.95 to 2.0 moles, and more preferably 0.98 to 1.5 moles, per 1 mole of the aromatic dihydroxy compound.

[0455] The prepolymer in a molten state manufactured from the above-described aromatic dihydroxy compound and the diaryl carbonate, i.e., the molten prepolymer refers to a molten substance in the polymerization process having a lower degree of polymerization than the aromatic branched polycarbonate having a target degree of polymerization manufactured from the aromatic dihydroxy compound and the diaryl carbonate, and can be an oligomer.

[0456] The average degree of polymerization of the molten prepolymer of the aromatic branched polycarbonate that can be manufactured using the manufacturing apparatus of the present embodiment for the aromatic branched polycarbonate is not particularly limited, and varies depending on the chemical structure thereof, and is generally about 2 to about 2,000.

[0457] The molten prepolymer used as a raw material for polymerization can be manufactured by a publicly known method.

[0458] (Catalyst)

[0459] The reaction for manufacturing the aromatic branched polycarbonate from the aromatic dihydroxy compound and the diaryl carbonate can be performed without adding a catalyst, but is performed in the presence of a catalyst as needed in order to increase the polymerization rate.

[0460] As the catalyst, there is no particular limitation as long as it is a catalyst used in the field.

[0461] As the catalyst, for example, the following can be listed: hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like; alkali metal salts, alkaline earth metal salts, quaternary ammonium salts of boron or aluminum hydrides such as lithium aluminum hydride, sodium borohydride, tetramethylammonium borohydride, and the like; hydrides of alkali metals and alkaline earth metals such as lithium hydride, sodium hydride, calcium hydride, and the like; alkoxides of alkali metals and alkaline earth metals such as lithium methoxide, sodium ethoxide, calcium methoxide, and the like; aryloxides of alkali metals and alkaline earth metals such as lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO-Ar-OLi, NaO-Ar-ONa (Ar is an aryl group), and the like; organic acid salts of alkali metals and alkaline earth metals such as lithium acetate, calcium acetate, sodium benzoate, and the like; zinc compounds such as zinc oxide, zinc acetate, zinc phenoxide, and the like; tin compounds such as boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate, tin oxide, dialkyl tin oxide, dialkyl tin carboxylate, tin acetate, ethyl tributoxy tin, and the like; lead compounds such as lead oxide, lead acetate, lead carbonate, basic lead carbonate, alkoxides or aryloxides of lead and organolead, and the like; quaternary ammonium salts, and the like, but are not limited thereto.

[0462] These catalysts can be used singly with only one kind, or two or more kinds in combination. In addition, the amount of use of these catalysts is usually in the range of 10 -10 mass% to 1 mass%, preferably in the range of 10 -9 mass% to 10 -1 mass%, further preferably in the range of 10 -8 mass% to 10 -2 mass%.

[0463] In the case of carrying out the melt ester exchange method, the used catalyst remains in the product aromatic branched polycarbonate, but these catalysts generally mostly have adverse effects on the polymer properties. Therefore, the amount of use of the catalyst is preferably reduced as much as possible. The guide of the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment contacts the falling type polymerization apparatus, and thus the amount of use of the catalyst can be reduced because the polymerization can be carried out efficiently. This is also one of the advantages of the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment, which enables the manufacture of the aromatic branched polycarbonate of high quality.

[0464] The aromatic branched polycarbonate manufactured by the manufacturing apparatus for the aromatic branched polycarbonate of the present embodiment has a repeating unit represented by the following formula.

[0465]

[0466] (In the formula, Ar is defined in the same manner as the above definition.)

[0467] ​Particularly preferred aromatic branched polycarbonates are aromatic branched polycarbonates containing 85 mol% or more of repeating units represented by the following formula in all repeating units.

[0468]

[0469] In addition, the terminal groups of the aromatic branched polycarbonate manufactured by the manufacturing apparatus for aromatic branched polycarbonates of the present embodiment generally contain hydroxyl groups or carbonate aryl ester groups represented by the following formula.

[0470]

[0471] (In the above formula, Ar 5 is defined in the same manner as the definition of Ar" above.)

[0472] The molar ratio of hydroxyl groups to carbonate aryl ester groups as the terminal groups of the aromatic branched polycarbonate is not particularly limited, and is generally in the range of hydroxyl groups:carbonate aryl ester groups = 95:5 to 5:95, preferably in the range of 90:10 to 10:90, and further preferably in the range of 80:20 to 20:80. Particularly preferred is an aromatic branched polycarbonate in which the ratio of phenyl carbonate groups in the terminal groups is 85 mol% or more.

[0473] As described above, the aromatic branched polycarbonate manufactured by the manufacturing apparatus for aromatic branched polycarbonates of the present embodiment is an aromatic branched polycarbonate having repeating units represented by general formula (1) in a main chain and a side chain, containing one or more branching structures represented by general formulas (2), (3), and (4) in the main chain and the side chain, the proportion of the total amount of substances of the branching structures with respect to the amount of substances of the repeating units represented by general formula (1) above being in the numerical range of 0.01 mol% to 0.5 mol%, containing one or more oligomers represented by general formulas (5), (6), and (7), the total mass of the oligomers being 0.6 mass% or less, and the ratio of the amount of substances of the oligomers represented by general formulas (5), (6) with respect to the total amount of substances of the oligomers being 60 mol% or less.

[0474] By using the manufacturing apparatus for aromatic branched polycarbonates of the present embodiment, it is possible to stably manufacture an aromatic branched polycarbonate having no variation in molecular weight for a long period of time.

[0475] Note that the manufacturing apparatus for aromatic branched polycarbonates of the present embodiment can be any manufacturing apparatus as long as it satisfies the above various conditions and has a mechanical strength corresponding thereto, and can be attached with any device and equipment having other functions required for continuous manufacturing operation of the aromatic branched polycarbonates.

[0476] Further, the apparatus for producing the aromatic branched polycarbonate of the present embodiment can be an apparatus in which a plurality of the above-mentioned guide-contacted flow-down polymerization apparatuses are combined, or can be an apparatus to which any device or equipment having a function other than polymerization is added.

[0477] In the apparatus for producing the aromatic branched polycarbonate of the present embodiment, a known catalyst deactivator described in International Publication No. 2005 / 121213, for example, can be used when producing the aromatic branched polycarbonate.

[0478] The catalyst deactivator is preferably used in a ratio of 0.5 to 50 moles, more preferably in a ratio of 0.5 to 10 moles, and further preferably in a ratio of 0.8 to 5 moles, per 1 mole of the transesterification catalyst. The catalyst deactivator can be added in the extruder, for example.

[0479] In the process of producing the aromatic branched polycarbonate using the apparatus for producing the aromatic branched polycarbonate of the present embodiment, various additives can be added, for example, in the second guide-contacted flow-down polymerization apparatuses 48A and 48B, in the post-stage apparatuses 50A and 50B, or in both. Figure 5 Further, the aromatic branched polycarbonate obtained in the second guide-contacted flow-down polymerization apparatuses 48A and 48B is sent out from the second guide-contacted flow-down polymerization apparatuses 48A and 48B to the post-stage apparatuses 50A and 50B in a molten state, and additives can be added in the post-stage apparatuses 50A and 50B.

[0480] The post-stage apparatuses 50A and 50B are not particularly limited as long as they are apparatuses that have conventionally received molten aromatic branched polycarbonates, and can include extruders, pelletizers, sieving machines, dryers, silos, packaging machines, and the like.

[0481] For example, the molten aromatic branched polycarbonate is supplied to an extruder, and in the extruder, other resins such as ABS or PET, additives such as heat-resistant stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, release agents, flame retardants, pigments or dyes of organic or inorganic, metal deactivators, antistatic agents, lubricants, nucleating agents, and the like, or any additives can be mixed.

[0482] These other resins and any additives can be used singly or in combination of two or more.

[0483] Further, the aromatic branched polycarbonate of the present embodiment can contain aliphatic dihydroxy compounds (diols) such as ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,10-decanediol; dicarboxylic acids such as succinic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, adipic acid, cyclohexanedicarboxylic acid, and terephthalic acid; hydroxy acids such as lactic acid, p-hydroxybenzoic acid, and 6-hydroxy-2-naphthoic acid; and the like.

[0484] As described above, by using the manufacturing apparatus of the aromatic branched polycarbonate of the present embodiment, the aromatic branched polycarbonate can be continuously manufactured.

[0485] The aromatic branched polycarbonate obtained by the manufacturing method of the aromatic branched polycarbonate of the present embodiment can be manufactured into a molded product by a prescribed molding process.

[0486] The molding process can be a publicly known molding process, and for example, an injection molding machine, an extrusion molding machine, a blow molding machine, a sheet molding machine, or the like can be used to mold the aromatic branched polycarbonate to obtain a molded product.

[0487] The obtained molded product can be used as a material for a wide range of uses such as automobiles, electricity, electronics, office automation (OA), optical media, building materials, and medical care.

[0488] According to the present embodiment, an aromatic branched polycarbonate having less coloration and good color tone stability to heat can be effectively provided.

[0489] Examples

[0490] Hereinafter, the present application will be specifically described using specific examples and comparative examples, but the present application is not limited by these examples and comparative examples.

[0491] Hereinafter, the raw materials of the aromatic branched polycarbonates manufactured in the following examples and comparative examples are shown.

[0492] [Raw Materials]

[0493] ((1) Aromatic dihydroxy compound)

[0494] BPA-1: Bisphenol A manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0495] ((2) Carbonic acid diaryl ester)

[0496] DPC-1: Diphenyl carbonate manufactured by the method described in International Publication No. 2006 / 006585

[0497] Hereinafter, the measurement methods of the physical properties and characteristics of the aromatic branched polycarbonates manufactured in the following examples and comparative examples are shown.

[0498] [Physical properties and characteristics]

[0499] ((1) Molecular weight, number average molecular weight (Mn))

[0500] As a measurement object, a particle of a prepolymer or an aromatic branched polycarbonate was measured using a gel permeation chromatograph (HLC-8320 GPC, manufactured by Tosoh Corporation, two of TSK-GEL Super Multipore HZ-M, RI detector) using tetrahydrofuran as an eluent at a temperature of 40°C.

[0501] The molecular weight of the prepolymer or the particle was calculated from a calibration curve of a standard monodisperse polystyrene (EasiVial, manufactured by VARIAN Corporation) using a conversion molecular weight calibration curve based on the following formula.

[0502] M PC = 0.3591M PS 1.0388

[0503] (In the formula, M PC represents the molecular weight of the aromatic branched polycarbonate, M PS represents the molecular weight of polystyrene.)

[0504] ((2) Measurement of hue)

[0505] Using a particle of an aromatic branched polycarbonate dried in a hot air drier at 120°C for 5 hours, a test piece having a length of 50 mm, a width of 90 mm, and a thickness of 3.0 mm was continuously molded using an injection molding machine under conditions of a cylinder temperature of 300°C and a mold temperature of 90°C, thereby obtaining a test piece.

[0506] The test piece was measured by a spectrophotometer (Vista, manufactured by HunterLab) by a transmission method under conditions of a D65 light source and a field angle of 10°, and the yellowness was expressed by a b* value (CIENo. 15 (ASTM E308) standard).

[0507] ((3) Molar ratio of oligomers represented by general formulas (5), (6), and (7) with respect to the total amount of substances of the oligomers)

[0508] 0.15 g of an aromatic branched polycarbonate was dissolved in 7 mL of tetrahydrofuran, and then about 15 g of methanol was added, and shaken by hand for 20 rounds, and then left to stand for 30 minutes.

[0509] Within 40 minutes after the standing, the supernatant was filtered using a filter having a pore size of 0.5 μm, and the peak intensity of each oligomer was measured using a reverse phase liquid chromatograph (UPLC, manufactured by WATERS Corporation, Japan).

[0510] In the reverse phase liquid chromatography, ACQUITY UPLC column: HSS T3 1.8 μm column (manufactured by WATERS Corporation, Japan) was used, and a mixed eluent containing methanol / distilled water at a mixing ratio of 85 / 15 was used as an eluent, and the measurement was performed at a column oven of 40°C.

[0511] The detection was performed using a UV detector at a wavelength of 210 nm.

[0512] ((4) Total mass ratio of the oligomers represented by general formulas (5), (6), and (7)

[0513] From the measurement results obtained in the molecular weight measurement according to the above (1), the area ratio of the molecular weight between 500 and 800 with respect to the entire molecular weight curve was calculated, and this was taken as the total mass ratio (mass %) of the above oligomers with respect to the mass of the aromatic branched polycarbonate.

[0514] ((5) Amount of substance of branched structure (mole %))

[0515] 55 mg of the aromatic branched polycarbonate was dissolved in 2 mL of tetrahydrofuran, and then 0.5 mL of a 5N potassium hydroxide methanol solution was added, and it was stirred at 25°C for 2 hours to completely hydrolyze it.

[0516] Then, 0.3 mL of concentrated hydrochloric acid was added, and the amount of substance of the branched structure represented by the above general formulas (2), (3), and (4) with respect to the amount of substance of the repeating unit represented by the above general formula (1) in the aromatic branched polycarbonate was measured using a reverse phase liquid chromatograph (LC-1100, manufactured by Agilent Corporation).

[0517] In the reverse phase liquid chromatography, Inertsil ODS-3 column (registered trademark: manufactured by GL Science Corporation) was used, and a mixed eluent containing methanol and 0.1% phosphoric acid aqueous solution was used as an eluent, the column oven was 40°C, and the measurement was performed under conditions in which the ratio of methanol / 0.1% phosphoric acid aqueous solution was gradually changed from 20 / 80 to 100 / 0.

[0518] The detection was performed using a UV detector at a wavelength of 300 nm, and the quantification was performed based on the absorbance coefficient of the standard substance.

[0519] ((6) Measurement of MI)

[0520] The measurement was performed using a melt flow tester (Mflow, manufactured by Zwick Roell Corporation) at 300°C under a load of 1.2 kg on the particles of the aromatic branched polycarbonate dried in a hot air dryer at 120°C for 5 hours (unit: g / 10 minutes) (ISO 1133 standard).

[0521] The average and standard deviation were calculated from the measurements taken every 2 hours (150 points) from 50 hours to 300 hours after the start of the production.

[0522] ((7) Hot air test)

[0523] The test piece was produced in the same manner as the test piece produced in the measurement of the color tone in (2) above, and the test piece was left in a Gill oven maintained at 120°C for 1,000 hours.

[0524] Then, the measurement of the color tone was performed, and the difference (Δb* value) between before and after the hot air test was calculated.

[0525] [Example 1]

[0526] Using Figure 5 The production apparatus for the aromatic branched polycarbonate shown in the configuration was used to produce the aromatic branched polycarbonate as follows.

[0527] In the production apparatus for the aromatic branched polycarbonate, the polymerization raw material and the catalyst were fed into the mixing tank 31, and mixed.

[0528] Next, the mixture was fed to the dissolving mixture storage tank 33A, 33B using the feed pump 32, and further pre-polymerized in the first polymerizer 35 using the feed pump 34A, 34B from the storage tank 33A, 33B.

[0529] The pre-polymer was then pre-polymerized in the second polymerizer 37 via the discharge gear pump 36, and the aromatic branched polycarbonate pre-polymer was obtained.

[0530] The aromatic branched polycarbonate pre-polymer was fed to the first inactive gas absorption device 39 via the feed pump 38, and the pre-polymer to which the inactive gas was absorbed was fed to the first guide contact flow polymerization device 42 after the feed pressure to the guide contact flow polymerization device was adjusted as needed using the pressure adjusting valve 41, and polymerized. At this time, phenol as a low molecular weight component was discharged from the exhaust port.

[0531] Note that, as the pressure adjusting valve 41, for example, a valve or the like can be exemplified as an example, but there is no limitation to the configuration as long as the solubility of the inactive gas can be adjusted. The same applies to the pressure adjusting valves 47A, 47B described below.

[0532] Next, the prepolymer of the aromatic branched polycarbonate is transported to the second non-active gas absorption device 44 via the supply pump 43, and then transported from the second non-active gas absorption device 44 using the supply pumps 46A, 46B. The supply pressure of the prepolymer of the non-active gas absorption device to the following guide contact flow down polymerization device is adjusted as needed using the pressure regulating valves 47A, 47B, and then transported to the connected second guide contact flow down polymerization devices 48A, 48B, and polymerized. Here, phenol is discharged from the exhaust port.

[0533] Then, transported using the supply pumps 49A, 49B, additives are added in the devices 50A, 50B in the rear stage, and thus the target aromatic branched polycarbonate is obtained.

[0534] Figure 1 A schematic diagram of the first and second non-active gas absorption devices 39, 44 is shown in FIG. 1.

[0535] Note that the device structure of the non-active gas absorption devices 39, 44 is substantially the same as the guide contact flow down polymerization devices 42, 48A, 48B described later, and thus the same symbols are used for the same parts.

[0536] For the first non-active gas absorption device 39, in the non-active gas absorption zone 15 as the internal space, the upper portion of the side housing 10 is cylindrical, the bottom housing 11 as the conical lower portion of the lower structure constituting the side housing 10 is an inverted cone, and the lower portion of the side housing 10 is a circular truncated cone. Figure 1 In FIG. 1, L = 500 cm, h = 400 cm, D = 200 cm, d = 20 cm, and C = 150°.

[0537] In addition, the outer diameter of the guide 4 provided in the non-active gas absorption zone 15 as the internal space is r = 0.3 cm, and the total external surface area S = 60 m 2 The diameter of the holes of the perforated plate 2 provided in the upper portion of the non-active gas absorption zone 15 as the internal space is about 0.2 cm.

[0538] In addition, the second non-active gas absorption device 44 is substantially the same shape as the first non-active gas absorption device 39 except that the diameter of the holes of the perforated plate is about 0.6 cm.

[0539] Figure 2 A schematic diagram of the guide contact flow down polymerization devices 42, 48A, 48B is shown in FIG. 2.

[0540] The first guide contact flow down polymerization device 42 has a flow path control member 20 in the shape of a disc with a thickness of about 2 cm and a guide 4 in the shape of a cylinder or a tube as shown in FIG. 3. Figure 3

[0541] ​Further, Figure 3 A schematic structural view showing that the guide contacts the upper portion of the guide 4 of the falling film polymerization apparatus is shown in FIG. 2.

[0542] In the guide-contacting falling film polymerization apparatus, the flow path control member 20 is suspended and fixed from the upper portion at a distance of about 8 cm from the upper inner wall surface 23 of the liquid supply zone 3.

[0543] Further, the inner side wall surface 22 of the liquid supply zone 3 is spaced apart from the flow path control member 20 by about 9 cm, and the porous plate 2 is spaced apart from the flow path control member 20 by about 8 cm.

[0544] Note that the peripheral edge portion of the disc-shaped flow path control member 20 is finely processed to be a semicircle with a radius of about 1 cm in a vertical cross section, and is designed so that liquid does not stagnate in the peripheral edge portion.

[0545] Further, the inner side wall surface 22 of the liquid supply zone is finely processed to be concave in a cross section of the connecting portion of the porous plate 2 as shown in FIG. 4, and the angle E of the rising portion thereof is about 170 degrees (°). Figure 4

[0546] The material of the guide-contacting falling film polymerization apparatus is stainless steel throughout.

[0547] The discharge pump 8 is preferably a gear pump in the case of a highly viscous concentrated liquid, and is a general liquid delivery pump in the case of a less viscous liquid.

[0548] The first guide-contacting falling film polymerizer 42 has a cylindrical side shell 10 and a conical bottom shell 11, and in the side shell 10, L = 950 cm and h = 850 cm. Figure 2

[0549] The inner diameter D of the side shell of the evaporation zone 5 is 400 cm, the inner diameter d of the liquid discharge port 7 of the conical bottom shell 11 is 20 cm, and C = 150 degrees.

[0550] The total external surface area S of the guide 4 as a whole is 750 m 2 .

[0551] The internal cross-sectional area A on the horizontal plane of the side shell 10 of the evaporation zone 5 as an internal space is 12.56 m 2 .

[0552] Further, the ratio of the above internal cross-sectional area A to the internal cross-sectional area B (m 2 ) on the horizontal plane of the liquid discharge port 7 is A / B = 400.

[0553] Further, D / d = 20.

[0554] ​​The ratio of the length L (cm) of the side shell of evaporation zone 5 to the inner diameter D (cm) mentioned above is L / D = 2.375.

[0555] In addition, the outer diameter r of the above-mentioned guide is 0.3 cm.

[0556] per 1m 2 Average number of holes in perforated plate 2 (holes / m) 2 N = approximately 500. The diameter of the holes in the perforated plate is approximately 0.2 cm.

[0557] The ratio of the upper area T of the porous plate 2, which includes the upper area of ​​the holes in the porous plate 2, to the total effective cross-sectional area Q of the holes is T / Q = approximately 1300.

[0558] The guide 4, which is closest to the inner wall of the evaporation zone 5, is spaced about 14 cm apart from the inner wall.

[0559] The volume V (approximately 2.03 m³) of space in the liquid supply zone 3, from the liquid receiving port 1 (the junction between the liquid receiving port and the upper inner wall of the liquid supply zone) to the upper surface of the perforated plate 2, is sufficient to hold the liquid. 3 The upper area T of the porous plate 2, which includes the upper area of ​​the holes in the porous plate 2, is approximately 12.56 m². 2 The ratio of V / T is approximately 0.162 (m).

[0560] The spatial volume Y of evaporation zone 5 is approximately 135m³. 3 .

[0561] The ratio of the volume V of liquid in the liquid supply zone 3, from the liquid receiving port 1 to the upper surface of the perforated plate 2, to the volume Y of the evaporation zone, is approximately 67.

[0562] In Example 1, the values ​​of the apparatus for manufacturing aromatic branched polycarbonate satisfy all of the above formulas (I) to (XV).

[0563] exist Figure 2 In the liquid supply zone 3, the liquid containing low-boiling-point substances supplied from the liquid receiving port 1 is... Figure 3 The liquid flows mainly from the periphery of the perforated plate 2 toward the center between the upper surface of the flow path control component 20 and the upper inner wall 23 of the liquid supply area 3, and between the inner side wall 22 of the supply area 3 and the flow path control component 20, while being evenly distributed to each guide 4 from the holes (21, etc.) of the perforated plate 2.

[0564] The lower part of the guide contact flow polymerization device has an inactive gas supply port 9, and the upper part has a vacuum exhaust port 6 (usually connected to a gas condenser and pressure reducing device) for extracting evaporates of low-boiling-point substances.

[0565] The outer side of the guide contact flow polymerization device is equipped with a jacket or a heating pipe for the heat medium, which enables the heat medium to be used to maintain a specified temperature.

[0566] The second guide contact the downstream polymerization units 48A and 48B. Figure 3 The structure shown has a disc-shaped flow path control component 20 and a guide component 4 with a thickness of about 2 cm.

[0567] The disc-shaped flow path control component 20 is suspended and fixed from the top at a distance of about 8 cm from the upper inner wall 23 of the liquid supply area 3.

[0568] In addition, the distance between the inner sidewall 22 of the liquid supply area 3 and the flow path control component 20 is about 9 cm, and the distance between the perforated plate 2 and the flow path control component 20 is about 8 cm.

[0569] It should be noted that the periphery of the disc-shaped flow control component 20 is finely machined into a semicircle with a vertical cross-section of about 1 cm in radius, and is designed so that liquid will not stagnate in the periphery.

[0570] Additionally, the cross-section of the connection between the inner sidewall 22 of the liquid supply zone 3 and the perforated plate 2 is as follows: Figure 4 The inner side shown is finely machined into a concave shape, and the angle E of its rising part is approximately 170 degrees (°).

[0571] The guide components of the downflow polymerization unit are all made of stainless steel.

[0572] A discharge pump 8 is provided at the lower part of the second guide contact flow polymerization device 48A, 48B. When the concentrated liquid has a high viscosity, a gear pump is preferred, and when the viscosity is not so high, a conventional liquid delivery pump is preferred.

[0573] The second guide contact flow polymerization device has a cylindrical side shell 10 and a conical bottom shell 11.

[0574] Regarding the second guide contact flow polymerization device, in Figure 2 In the given information, L = 1,000 cm and h = 900 cm.

[0575] The inner diameter D of the side shell 10 of the evaporation zone 5 is 500 cm, and the inner diameter d of the liquid outlet 7 of the conical bottom shell 11 is 40 cm, C = 155 degrees (°).

[0576] The total external surface area of ​​guide component 4 is S = 250m² 2 .

[0577] The internal cross-sectional area A of the side shell 10, which serves as the evaporation zone 5 within the interior space, on its horizontal plane is 19.625 m².2 .

[0578] In addition, the aforementioned internal cross-sectional area A and the internal cross-sectional area B (m²) on the horizontal plane of the liquid outlet 7 2 The ratio A / B is 156.25.

[0579] Additionally, D / d = 12.5.

[0580] The ratio of the length L (cm) of the side shell of evaporation zone 5 to the inner diameter D (cm) mentioned above is L / D = 2.

[0581] In addition, the outer diameter r of the above-mentioned guide is 0.3 cm.

[0582] per 1m 2 Average number of holes in perforated plate 2 (holes / m) 2 N = approximately 140. The diameter of the holes in the perforated plate is approximately 0.4 cm.

[0583] The ratio of the upper area T of the porous plate 2, which includes the upper area of ​​the holes in the porous plate 2, to the total effective cross-sectional area Q of the holes is T / Q = approximately 470.

[0584] The guide 4, which is closest to the inner wall of the evaporation zone 5, is spaced about 15 cm from the inner wall.

[0585] The liquid supply zone 3, extending from the liquid receiving port 1 (the junction between the liquid receiving port and the upper inner wall of the liquid supply zone) to the upper surface of the perforated plate 2, contains a spatial volume V (approximately 3.17 m³) in which the liquid can exist. 3 The upper area T of the porous plate containing the holes (approximately 19.63 m²) is the same as the upper area of ​​the porous plate containing the holes. 2 The value of V / T is approximately 0.161 (m).

[0586] The spatial volume Y of evaporation zone 5 is approximately 222.8 m³. 3 The ratio of the volume V of liquid in the liquid supply zone 3, from the liquid receiving port 1 to the upper surface of the perforated plate 2, to the volume Y of the evaporation zone, is approximately 70.

[0587] In Example 1, the second guide in the aromatic branched polycarbonate manufacturing apparatus contacts the downflow polymerization apparatus and satisfies all of the above formulas (I) to (XV).

[0588] The structures of the second guide contact downflow polymerization apparatuses 48A and 48B are the same as those of the first guide contact downflow polymerization apparatus 42 in the liquid supply zone 3.

[0589] In addition, the total external surface area S1 (m²) of the guide 4 of the first guide in the downflow polymerization apparatus 42 is S1. 2) The ratio of the total outer surface area S2 (m 2 ) of the guide 4 of the second guide-contacting falling polymerization apparatus (48A, 48B) to the total outer surface area S1 (m

[0590] The material of the above-mentioned inactive gas absorption apparatus, the first guide-contacting falling polymerization apparatus, and the second guide-contacting falling polymerization apparatus is stainless steel except for the discharge pump 8.

[0591] The aromatic branched polycarbonate was manufactured using a manufacturing apparatus for aromatic branched polycarbonate, which is shown in Figure 5 The two inactive gas absorption apparatuses (the first inactive gas absorption apparatus 39, the second inactive gas absorption apparatus 44) and the two guide-contacting falling polymerization apparatuses (the first guide-contacting falling polymerization apparatus 42, the second guide-contacting falling polymerization apparatus 48A, 48B) were connected in series in the order of the first inactive gas absorption apparatus 39, the first guide-contacting falling polymerization apparatus 42, the second inactive gas absorption apparatus 44, and the second guide-contacting falling polymerization apparatus 48A, 48B, which were arranged in parallel.

[0592] The molten diphenyl carbonate (DPC-1) at 160°C was poured into the mixing tank 31 (the content amount was 120 m 3 ) at 160°C.

[0593] Next, with respect to 45 tons of the bisphenol A (BPA-1), 120 mass ppb of potassium hydroxide as a catalyst was added, and the bisphenol A was poured into the mixing tank for 1.8 hours while the temperature of the mixed solution in the mixing tank was maintained at 100°C or higher.

[0594] The amount of the bisphenol A poured was 45.3 tons.

[0595] Next, 6.67 tons of diphenyl carbonate was additionally poured so that the molar ratio of the diphenyl carbonate to the above-mentioned bisphenol A was 1.10. Note that the amount of the diphenyl carbonate poured was weighed using a Coriolis mass flowmeter, and the amount of the bisphenol A poured was weighed using a weighing sensor-equipped measuring hopper.

[0596] At the time when the temperature of the above-mentioned mixed solution reached 180°C, it was transported to the dissolving mixture tank (the content amount was 120 m 3 ) 33A for 1 hour.

[0597] The reaction mixture held in the dissolved mixture tank 33A for 4 to 6 hours was filtered at a flow rate of 14 tons / hour using two polymer filters (not shown) having different pore diameters arranged in series between the dissolved mixture tank 33A and the stirred tank first polymerizer 35. The pore diameter of the upstream side was 5 μm and the pore diameter of the downstream side was 2.5 μm.

[0598] The filtered reaction mixture was heated using a preheater (not shown) and supplied to the stirred tank first polymerizer 35. The liquid temperature at the outlet of the preheater was 230°C.

[0599] At the time when the liquid level of the reaction mixture in the dissolved mixture tank 33A fell below a prescribed value, the supply source of the reaction mixture to the stirred tank first polymerizer 35 was switched from the dissolved mixture tank 33A to the dissolved mixture tank 33B. The supply of the reaction mixture to the stirred tank first polymerizer 35 was continuously carried out by repeating the operation of alternately switching the supply source of the dissolved mixture tank 33A and 33B every 3.9 hours.

[0600] Note that both the dissolved mixture tanks 33A and 33B were provided with an internal coil and a jacket and maintained at 180°C.

[0601] In the stirred tank first polymerizer 35 and the stirred tank second polymerizer 37, the reaction mixture was polymerized while removing the generated phenol under reduced pressure to obtain a prepolymer.

[0602] The temperature of the stirred tank first polymerizer 35 at this time was 230°C and the pressure was 13.3 kPaA, and the temperature of the stirred tank second polymerizer 37 was 265°C and the pressure was 2.66 kPaA.

[0603] The obtained molten prepolymer of aromatic branched polycarbonate (number average molecular weight Mn was 2,200) was continuously supplied from the liquid receiving port 1 of the first inactive gas absorption device to the liquid supply zone 3 using a supply pump 38.

[0604] The above prepolymer continuously supplied to the inactive gas absorption zone 15 as an internal space through the porous plate 2 as a distribution plate of the first inactive gas absorption device 39 was caused to flow down along the guide 4 while being subjected to absorption of the inactive gas.

[0605] The inactive gas absorption zone 15 as an internal space of the first inactive gas absorption device 39 was supplied with nitrogen gas from the inactive gas supply port 9 and maintained at 180 kPaA.

[0606] The molten prepolymer (containing 0.04 NL of nitrogen per 1 kg of the molten prepolymer) falling down from the lower portion of the guide 4 to the conical lower portion 11 of the casing of the first non-active gas absorption device 39 is continuously discharged by the discharge pump 8 (corresponding to symbol 40 in Figure 5 the above) so that the amount at the bottom of the device is kept substantially constant, the pressure of the molten prepolymer entering the valve is maintained at 75 kPa A by the pressure regulating valve 41 located at the liquid receiving port 1 of the first guide contact flow down polymerization device 42, and is continuously supplied into the liquid supply zone 3 through the liquid receiving port 1 of the first guide contact flow down polymerization device 42.

[0607] The evaporation zone 5, which is the internal space of the first guide contact flow down polymerization device 42, is kept at a pressure of 800 Pa A by the vacuum exhaust port 6.

[0608] The molten prepolymer (having a number average molecular weight Mn of 4,700) of the aromatic branched polycarbonate with increased degree of polymerization falling down from the lower portion of the guide 4 to the conical lower portion 11 of the casing of the first guide contact flow down polymerization device 42 is continuously extracted from the liquid discharge port 7 by the discharge pump 8 (corresponding to symbol 43 in Figure 5 the above) at a constant flow rate so that the amount at the bottom is kept substantially constant, and is then continuously supplied into the liquid supply zone 3 of the second non-active gas absorption device 44.

[0609] The above molten prepolymer is continuously supplied into the non-active gas absorption zone 15, which is the internal space, through the perforated plate 2, which is the distribution plate of the second non-active gas absorption device 44.

[0610] The molten prepolymer is caused to flow down along the guide 4 to undergo absorption of non-active gas.

[0611] The non-active gas absorption zone 15, which is the internal space of the second non-active gas absorption device 44, is supplied with nitrogen from the non-active gas supply port 9 and kept at 75 kPa A.

[0612] The molten prepolymer (containing 0.05 NL of nitrogen per 1 kg of the molten prepolymer) falling down from the lower portion of the guide 4 to the bottom casing 11 of the conical lower portion of the casing of the second non-active gas absorption device is divided into two portions (split in a ratio of 50:50) by the three-way polymer valve (45), is continuously discharged by the discharge pump 8 (corresponding to symbols 46A, 46B in Figure 5 the above) at a constant amount so that the amount at the bottom is kept substantially constant, the pressure of the molten prepolymer entering the valve is maintained at 220 kPa A by the pressure regulating valves (47A, 47B) located at the liquid receiving ports 1 of the second guide contact flow down polymerization devices 48A, 48B, and is continuously supplied into each of the liquid supply zones 3.

[0613] The molten prepolymer continuously supplied to the evaporation zone 5 as an internal space along the guide 4 by the porous plate 2 as the second guide contacting the distribution plate in the falling line type polymerization apparatus is caused to flow down while the polymerization reaction is carried out.

[0614] The evaporation zone 5 as the internal space of the falling line type polymerization apparatus contacted by the second guide is maintained at a pressure of 120 PaA respectively through the vacuum exhaust port 6.

[0615] The aromatic branched polycarbonate dropped from the lower portion of the guide 4 to the bottom housing 11 as the conical lower portion of the housing of the falling line type polymerization apparatus contacted by the second guide is continuously drawn out from the rear stage apparatus (50A, 50B) in the form of a strand in such a manner that the amount at the bottom is substantially constant using the discharge pump 8 (49A, 49B), and is cut after cooling, thereby obtaining the aromatic branched polycarbonate in the form of a pellet.

[0616] The production amount was 4.0 tons / hour (total 8.0 tons / hour) respectively.

[0617] The additive was not added.

[0618] The branched amount, oligomer amount, color, and hot air test pellet were collected 150 hours after the start of the production.

[0619] Each measurement or test was performed using the aromatic branched polycarbonate obtained from the rear stage apparatus 50A.

[0620] Note that, for the rear stage apparatus 50B, the production conditions were the same as the aromatic branched polycarbonate obtained in the rear stage apparatus 50A, and therefore each measurement or test was not performed.

[0621] [Example 2], [Comparative Examples 1, 3]

[0622] The molar ratio of DPC-1 to BPA-1, the catalyst addition amount, the reaction mixture supply amount to the stirred tank type first polymerizer 35, and the reaction temperature of the falling line type polymerization apparatus contacted by the second guide were changed to those described in Table 1 below, and otherwise the same as in the above Example 1, thereby obtaining the aromatic branched polycarbonate in the form of a pellet.

[0623] The production conditions and measurement and test results are shown in Table 1.

[0624] [Example 3]

[0625] Instead of the pressure regulating valves 41, 47A, 47B, pipes having the same inner diameter as the pipes through which the first and second guide-contacted flow-down polymerization devices are supplied are provided, and the same procedure as in Example 1 is followed, except that the pressure regulating valves are not used, to obtain a particulate aromatic branched polycarbonate. Note that the pressure gauges are provided at the same positions as in Example 1.

[0626] The manufacturing conditions and the measured and tested results are shown in Table 1.

[0627] [Example 4]

[0628] Nitrogen gas is supplied to the inactive gas absorption zone 15, which is the internal space of the first and second inactive gas absorption devices, and is adjusted to 180 kPaA and 200 kPaA, respectively, and then the supply of nitrogen gas is stopped. After the pressure of the inactive gas absorption zone 15, which is the internal space of each, reaches a constant value (in a state where no nitrogen gas is absorbed), the time when 50 hours have elapsed is taken as the start of the production, and the same procedure as in Example 1 is followed, except that the pressure regulating valves are not used, to obtain a particulate aromatic branched polycarbonate.

[0629] The manufacturing conditions and the measured and tested results are shown in Table 1.

[0630] [Example 5]

[0631] Instead of the pressure regulating valves 41, 47A, 47B, pipes having the same inner diameter as the pipes through which the first and second guide-contacted flow-down polymerization devices are supplied are provided, and the same procedure as in Example 4 is followed, except that the pressure regulating valves are not used, to obtain a particulate aromatic branched polycarbonate. (The pressure gauges are provided at the same positions as in Example 1)

[0632] The manufacturing conditions and the measured and evaluated results are shown in Table 1.

[0633] [Comparative Example 2]

[0634] The catalyst addition amount, the reaction mixture supply amount to the first polymerizer 35, which is a stirred tank, the pressure of the first guide-contacted flow-down polymerization device, and the reaction temperature and pressure of the second guide-contacted flow-down polymerization device are changed to those described in Table 1 below, and the same procedure as in Example 5 is followed, except that the pressure regulating valves are not used, to obtain a particulate aromatic branched polycarbonate.

[0635] The manufacturing conditions and the measured and tested results are shown in Table 1.

[0636]

[0637] This application is based on Japanese Patent Application (Japanese Patent Application No. 2021-051384) filed on March 25, 2021, in the Japan Patent Office, the content of which is incorporated herein by reference in its entirety.

[0638] Industrial applicability

[0639] The aromatic branched polycarbonate of the present application has industrial applicability in the field of using high-quality aromatic branched polycarbonates as materials.

[0640] Explanation of reference numerals

[0641] 1 liquid receiving port

[0642] 2 porous plate

[0643] 3 liquid supply area

[0644] 4 guide

[0645] 5 evaporation area as an internal space

[0646] 6 vacuum exhaust port

[0647] 7 liquid discharge port

[0648] 8 discharge pump

[0649] 9 non-active gas supply port

[0650] 10 side housing

[0651] 11 bottom housing

[0652] 12 discharge port

[0653] 15 non-active gas absorption area as an internal space

[0654] 20 flow path control member

[0655] 21 hole portion of the porous plate

[0656] 22 internal side wall surface of the liquid supply area

[0657] 23 upper internal wall surface of the liquid supply area

[0658] 31 mixing tank

[0659] 32, 34A, 34B delivery pump

[0660] 33A, 33B dissolved mixture storage tank

[0661] 35 first polymerizer

[0662] 36 discharge gear pump

[0663] 37 second polymerizer

[0664] 38, 40, 43, 46A, 46B, 49A, 49B feed pump

[0665] 39 first non-reactive gas absorbing device

[0666] 41, 47A, 47B pressure regulating valve

[0667] 42 first guide contact flow down polymerization device

[0668] 44 second non-reactive gas absorbing device

[0669] 45 three-way polymer valve

[0670] 48A, 48B second guide contact flow down polymerization device

[0671] 50A equipment of rear section

[0672] 50B equipment of rear section

Claims

1. An aromatic branched polycarbonate, wherein, The aromatic branched polycarbonate satisfies the following conditions (i) to (iii): <Condition (i)> The main chain and branches contain repeating units as shown in the following general formula (1). The main chain and branches contain one or more branched structures represented by the following general formulas (2), (3) and (4). The total amount of substance in the branched structure is in the ratio of the amount of substance of the repeating unit represented by the following general formula (1) to 0.01 mol% to 0.5 mol%. In formulas (1), (2), (3) and (4), Ar represents a divalent aromatic group and Ar' represents a trivalent aromatic group; <Condition (ii)> The aromatic branched polycarbonate contains one or more oligomers represented by the following general formulas (5), (6), and (7), wherein the total mass of the oligomers relative to the mass of the aromatic branched polycarbonate is less than 0.6% by mass. H-(O-Ar-OC(=O)-)2-OAr” (5) H-(O-Ar-OC(=O)-)2-O-Ar-OH (6) Ar”OC(=O)-(O-Ar-OC(=O)-)2-OAr” (7) In formulas (5), (6) and (7), Ar represents a divalent aromatic group, and Ar” represents an aromatic terminal group; <Condition (iii)> The ratio of the total amount of the oligomers represented by the general formulas (5) and (6) to the total amount of the oligomers is 60 mol% or less.

2. The aromatic branched polycarbonate according to claim 1, wherein, In the aforementioned <condition (i)>, the ratio of the total amount of the branched structure to the amount of the repeating unit represented by the above general formula (1) is 0.05 mol% to 0.4 mol%. In condition (ii), the ratio of the total mass of the oligomers to the mass of the aromatic branched polycarbonate is 0.3% by mass or less. In the <condition (iii)>, the ratio of the total amount of the oligomers represented by the above general formulas (5) and (6) to the total amount of the oligomers is 30 mol% or less.

3. The aromatic branched polycarbonate according to claim 1 or 2, wherein, In the <condition (i)>, the total amount of the branched structure is 0.2 mol% to 0.3 mol% relative to the amount of the repeating unit represented by the above general formula (1).

4. The aromatic branched polycarbonate according to claim 1, wherein, In the <condition (ii)>, the ratio of the total mass of the oligomers to the mass of the aromatic branched polycarbonate is less than 0.5% by mass.

5. The aromatic branched polycarbonate according to claim 4, wherein, In the <condition (ii)>, the ratio of the total mass of the oligomers to the mass of the aromatic branched polycarbonate is less than 0.4% by mass.

6. The aromatic branched polycarbonate according to claim 1 or 2, wherein, In the <condition (ii)>, the ratio of the total mass of the oligomers to the mass of the aromatic branched polycarbonate is 0.01% by mass or more.

7. The aromatic branched polycarbonate according to claim 6, wherein, In the <condition (ii)>, the ratio of the total mass of the oligomers to the mass of the aromatic branched polycarbonate is 0.05% by mass or more.

8. The aromatic branched polycarbonate according to claim 6, wherein, In the <condition (ii)>, the ratio of the total mass of the oligomers to the mass of the aromatic branched polycarbonate is 0.1% by mass or more.

9. The aromatic branched polycarbonate according to claim 1, wherein, In the <condition (iii)>, the ratio of the total amount of the oligomers represented by the above general formulas (5) and (6) to the total amount of the oligomers is 50 mol% or less.

10. The aromatic branched polycarbonate according to claim 1 or 2, wherein, In the <condition (iii)>, the ratio of the total amount of the oligomers represented by the above general formulas (5) and (6) to the total amount of the oligomers is 10 mol% or more.

11. The aromatic branched polycarbonate according to claim 1 or 2, wherein, Ar represents substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, or substituted or unsubstituted pyridylene.

12. The aromatic branched polycarbonate according to claim 1 or 2, wherein, Ar is a group represented by the following formula. -On 1 -Y-On 2 - In the formula, Ar 1 and Ar 2 Each of these groups independently represents a divalent carbon cyclic or heterocyclic aromatic group with 5 to 70 carbon atoms that can be substituted by one or more substituents selected from halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, and nitro groups. Y represents a divalent alkane group with 1 to 30 carbon atoms.

13. The aromatic branched polycarbonate according to claim 1 or 2, wherein, Ar is a group represented by the following formula. In the above formula, R 7 R 8 Each is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a cycloalkyl group with 5 to 10 cyclic carbon atoms, or a phenyl group, where m and n are integers from 1 to 4. When m is 2 to 4, each R... 7 Each can be the same or different. When n is 2 to 4, R 8 They can be the same or different.

14. The aromatic branched polycarbonate according to claim 1 or 2, wherein, Ar is a group represented by the following formula. -Ar 1 -Z-Ar 2 - In the formula, Ar 1 and Ar 2 Each of these groups independently represents a divalent carbocyclic or heterocyclic aromatic group with 5 to 70 carbon atoms that can be substituted by one or more substituents selected from halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, and nitro groups. Z represents a single bond or -O-, -CO-, -S-, -SO2-, -SO-, -COO-, -CON(R) 1 )-, R 1 It can represent hydrogen, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 cyclic carbon atoms, carbocyclic aromatic groups with 5 to 10 cyclic carbon atoms, or carbocyclic aralkyl groups with 6 to 10 carbon atoms.

15. The aromatic branched polycarbonate according to claim 12, wherein, Ar 1 and Ar 2 Each can be independently represented as a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted pyridylene.

16. The aromatic branched polycarbonate according to claim 1 or 2, wherein, Ar' is a group in which one of the hydrogen atoms of the divalent aromatic group is a bond point.

17. The aromatic branched polycarbonate according to claim 1 or 2, wherein, "Ar" represents a monovalent aromatic group with 5 to 20 carbon atoms that can be replaced by one or more substituents selected from halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, and nitro groups.

18. The aromatic branched polycarbonate according to claim 17, wherein, "Ar" represents phenyl, naphthyl, biphenyl, or pyridyl, wherein one or more hydrogen atoms of the phenyl, naphthyl, biphenyl, or pyridyl group may be substituted by one or more substituents selected from halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, phenyl, phenoxy, vinyl, cyano, ester, amide, and nitro groups.

19. The aromatic branched polycarbonate according to claim 1 or 2, wherein, The melt index (MI) of the aromatic branched polycarbonate, measured at 300°C and under a load of 1.2 kg, was 0.5 g / 10 min to 40 g / 10 min.

20. The aromatic branched polycarbonate according to claim 19, wherein, The melt index (MI) of the aromatic branched polycarbonate, measured at 300°C and under a load of 1.2 kg, was 0.5 g / 10 min to 20 g / 10 min.

21. The aromatic branched polycarbonate according to claim 19, wherein, The melt index (MI) of the aromatic branched polycarbonate, measured at 300°C and under a load of 1.2 kg, was 1 g / 10 min to 15 g / 10 min.

22. The aromatic branched polycarbonate according to claim 19, wherein, The melt index (MI) of the aromatic branched polycarbonate, measured at 300°C and under a load of 1.2 kg, was 2 g / 10 min to 12 g / 10 min.

23. The aromatic branched polycarbonate according to claim 1 or 2, wherein, The aromatic branched polycarbonate contains 0.001 ppm to 1 ppm of alkali metals and / or alkaline earth metals, calculated as metal elements.

24. The aromatic branched polycarbonate according to claim 23, wherein, The content of the alkali metal and / or alkaline earth metal is 0.005 ppm to 0.5 ppm.

25. The aromatic branched polycarbonate according to claim 23, wherein, The content of the alkali metal and / or alkaline earth metal is 0.01 ppm to 0.1 ppm.

26. The aromatic branched polycarbonate according to claim 1 or 2, wherein, The halogen content in the aromatic branched polycarbonate is less than 10 ppb.

27. The aromatic branched polycarbonate according to claim 26, wherein, The halogen content in the aromatic branched polycarbonate is less than 5 ppb.

28. The aromatic branched polycarbonate according to claim 26, wherein, The halogen content in the aromatic branched polycarbonate is less than 1 ppb.

29. A method for manufacturing an aromatic branched polycarbonate, comprising the method for manufacturing the aromatic branched polycarbonate according to any one of claims 1 to 28, wherein, The manufacturing method comprises the following steps: A process in which a nitrogen-absorbed aromatic branched polycarbonate prepolymer is maintained at 15 kPaA to 200 kPaA and fed to a flow-through polymerization unit that forms part of an aromatic branched polycarbonate manufacturing apparatus; and The process of causing the prepolymer to flow down the outer surface of a guide that does not have its own heating source, and causing low-boiling-point substances to evaporate.

30. The method for manufacturing aromatic branched polycarbonate according to claim 29, wherein, The prepolymer of aromatic branched polycarbonate that has absorbed nitrogen gas is kept at 20 kPaA to 150 kPaA.

31. The method for manufacturing aromatic branched polycarbonate according to claim 29 or 30, wherein, The prepolymer of aromatic branched polycarbonate that has absorbed nitrogen gas is kept at 20 kPaA to 100 kPaA.

32. The method for manufacturing aromatic branched polycarbonate according to claim 29 or 30, wherein, The evaporation of the low-boiling-point substance is carried out using a guide-type contact downflow polymerization apparatus, wherein the guide-type contact downflow polymerization apparatus satisfies the following conditions (1) to (9): <Condition (1)> The guide contact flow polymerization apparatus includes: a liquid receiving port; a liquid supply area for supplying liquid to the guides in the evaporation zone through a perforated plate; and an evaporation zone having a plurality of guides extending downward from the perforated plate within a space surrounded by the perforated plate, a side shell, and a bottom shell. A vacuum exhaust port is provided in the evaporation zone; And a liquid outlet, wherein the liquid outlet is located at the lowest part of the bottom housing; <Condition (2)> A flow path control component is provided in the liquid supply area, and the flow path control component has the function of causing the liquid supplied from the liquid receiving port to the perforated plate to flow from the periphery of the perforated plate to the center in the liquid supply area. <Condition (3)> The internal cross-sectional area A(m²) on the horizontal plane of the side shell of the evaporation zone 2 ) satisfies the following equation (I): 0.7≤A≤300 Formula (I); <Condition (4)> The internal cross-sectional area A (m 2 The internal cross-sectional area B (m²) on the horizontal plane of the liquid outlet. 2 The ratio of ) satisfies the following equation (II): Equation (II): 20 ≤ A / B ≤ 1000; <Condition (5)> The bottom shell constituting the bottom of the evaporation zone is connected to the upper side shell inside the evaporation zone at an angle C degrees (°), and the angle C degrees satisfies the following formula (III): 110≤C≤165 Equation (III); <Condition (6)> The length h (cm) of the guide element satisfies equation (IV): Equation (IV): 150≤h≤5000; <Condition (7)> The total external surface area S(m²) of the plurality of guide elements 2 Satisfying equation (V): Equation (V) is given by equation (V) where 2 ≤ S ≤ 50000. <Condition (8)> per 1m 2 The average number of holes N (holes / m) in the perforated plate 2 Satisfying equation (VI): Equation (VI): 50≤N≤3000; <Condition (9)> The upper area T(m²) of the porous plate, including the upper area of ​​the holes in the porous plate. 2 The sum of Q(m) and the effective cross-sectional area of ​​the hole 2 The ratio of ) satisfies the following equation (VII): 50≤T / Q≤3000 Equation (VII).

33. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the aforementioned <condition (5)>, 120≤C≤165.

34. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the aforementioned <condition (5)>, 135≤C≤165.

35. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the <condition (6)>, 200≤h≤3000.

36. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the <condition (6)>, 400≤h≤2500.

37. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the aforementioned <condition (7)>, 10 ≤ S ≤ 40000.

38. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the aforementioned <condition (7)>, 15≤S≤30000.

39. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the <condition (8)>, 70≤N≤2000.

40. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the <condition (8)>, 100≤N≤1000.

41. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the aforementioned <condition (9)>, 100≤T / Q≤2500.

42. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, In the aforementioned <condition (9)>, 250≤T / Q≤1500.

43. The method for manufacturing aromatic branched polycarbonate according to claim 29 or 30, wherein, The amount of liquid after evaporation is more than 1 ton per hour.

44. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The angle E (°) formed between the inner sidewall of the liquid supply zone and the perforated plate satisfies the following formula (VIII): 100≤E<180 Equation (VIII).

45. The method for manufacturing aromatic branched polycarbonate according to claim 44, wherein, 120≤E＜180。 46. ​​The method for manufacturing aromatic branched polycarbonate according to claim 44 or 45, wherein, 145≤E＜180。 47. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The distance K (cm) between the guide member and the inner wall surface of the side shell closest to the evaporation zone satisfies the following formula (IX): Equation (IX) is given by 5≤K≤50.

48. The method for manufacturing aromatic branched polycarbonate according to claim 47, wherein, 10≤K≤40。 49. The method for manufacturing aromatic branched polycarbonate according to claim 47 or 48, wherein, 12≤K≤30。 50. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The side shell of the evaporation zone is cylindrical with an inner diameter D (cm) and a length L (cm). The bottom shell connected to the lower part of the side shell is conical. The liquid outlet at the bottom of the conical bottom shell is cylindrical with an inner diameter d (cm). The terms D, L, and d satisfy the following equations (X), (XI), (XII), and (XIII): Equation (X) is given by equation (X) with a minimum value of 100 ≤ D ≤ 1800. 5≤D / d≤50 Equation (XI) 0.5≤L / D≤30 Formula (XII) h-20≤L≤h+300 Formula (XIII) In formula (XIII), h (cm) represents the length of the guide.

51. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The volume V(m³) of liquid that can exist in the liquid supply area from the liquid inlet to the upper surface of the perforated plate. 3 The upper area T(m²) of the porous plate containing the holes of the porous plate. 2 ) satisfies the following equation (XIV): 0.02(m)≤V / T≤0.5(m) Equation (XIV).

52. The method for manufacturing aromatic branched polycarbonate according to claim 51, wherein, 0.05(m)≤V / T≤0.4(m).

53. The method for manufacturing aromatic branched polycarbonate according to claim 51 or 52, wherein, 0.1(m)≤V / T≤0.3(m).

54. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The liquid supply area has a spatial volume V(m) capable of holding liquid. 3 ) and the spatial volume Y (m) of the evaporation zone 3 The following equation must be satisfied: 10≤Y / V≤500.

55. The method for manufacturing aromatic branched polycarbonate according to claim 54, wherein, 15≤Y / V≤400.

56. The method for manufacturing aromatic branched polycarbonate according to claim 54 or 55, wherein, 20≤Y / V≤300.

57. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, At least one of the guides is a cylindrical guide with an outer diameter r (cm) or a tubular guide that prevents liquid and / or gaseous substances from entering the inside of the guide, and The outer diameter r satisfies the following formula (XV): 0.1≤r≤1 Equation (XV).

58. The method for manufacturing aromatic branched polycarbonate according to claim 57, wherein, 0.15≤r≤0.8。 59. The method for manufacturing aromatic branched polycarbonate according to claim 57 or 58, wherein, 0.2≤r≤0.6。 60. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The guide contact downflow polymerization apparatus has a plurality of guides, and the plurality of guides are joined together using a support material.

61. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, The plurality of guides are selected from any one of the following groups: a grid-like or mesh-like guide obtained by fixing each guide with a lateral support material; a three-dimensional guide obtained by arranging a plurality of grid-like or mesh-like guides in front and behind and fixing these guides with a lateral support material; and a climbing frame-like three-dimensional guide obtained by fixing each of the plurality of guides in front, behind, left, and right with a lateral support material.

62. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, At least one guide contact flow polymerization device that satisfies the conditions (1) to (9) is further connected to the guide contact flow polymerization device, and two or more guide contact flow polymerization devices are connected in series, in parallel, or in a combination of series and parallel.

63. The method for manufacturing aromatic branched polycarbonate according to claim 62, wherein, A further guide contact flow polymerization device is connected to the guide contact flow polymerization device, and The total external surface area S1(m²) of the guide member of the downflow polymerization apparatus is S1. 2 The total external surface area S2 (m²) of the guide of the downstream polymerization apparatus and the further connected guide are in contact with each other. 2 ) satisfies the following formula (XVI): 1≤S1 / S2≤20 (XVI).

64. The method for manufacturing aromatic branched polycarbonate according to claim 63, wherein, 1.5≤S1 / S2≤15.

65. The method for manufacturing aromatic branched polycarbonate according to claim 32, wherein, An inert gas absorption device is provided for absorbing inert gases from the molten prepolymer of aromatic branched polycarbonate supplied to the guide before contacting the downstream polymerization apparatus. The pressure of the molten prepolymer that has absorbed the inert gas in the supply pipe of the molten prepolymer between the inert gas absorption device and the guide contact downflow polymerization device is maintained at 15 kPaA to 200 kPaA using a pressure regulating valve located immediately before the inlet of the guide contact downflow polymerization device, and the molten prepolymer is supplied to the guide contact downflow polymerization device.

66. The method for manufacturing aromatic branched polycarbonate according to claim 63 or 65, wherein, The guide contact underflow polymerization device is further connected to the guide contact underflow polymerization device. An inert gas absorption device is provided for absorbing inert gases from the molten prepolymer of aromatic branched polycarbonate supplied to each guide before it contacts the downflow polymerization unit. A pressure regulating valve is installed immediately before the inlet of each of the guide contact downflow polymerization devices. The pressure of the molten prepolymer that has absorbed the inactive gas in the supply pipeline of the molten prepolymer between the inactive gas absorption device and each of the guide contact downflow polymerization devices is maintained at 15 kPaA to 200 kPaA and supplied.

67. The method for manufacturing aromatic branched polycarbonate according to claim 65, wherein, The pressure Pg at which the molten prepolymer absorbs the inert gas is related to the number-average molecular weight M1 of the molten prepolymer before absorbing the inert gas by the following equation: Pg>4×10 12 × M1 -2.6871 ...

68. The method for manufacturing aromatic branched polycarbonate according to claim 29 or 30, wherein, The prepolymer of the aromatic branched polycarbonate is made from an aromatic dihydroxy compound and a diaryl carbonate.

69. An apparatus for manufacturing aromatic branched polycarbonate, the apparatus comprising: A guide-contact downflow polymerization apparatus that allows prepolymers of aromatic branched polycarbonate to flow down the outer surface of a guide that has no heating source of its own, during which low-boiling-point substances evaporate; and An inert gas absorption device is provided for absorbing inert gases from the molten prepolymer of aromatic branched polycarbonate supplied to the guide before contacting the downstream polymerization apparatus. The guide contact flow polymerization device satisfies the following conditions (1) to (9) The manufacturing apparatus has a pressure regulating valve that controls the pressure of the molten prepolymer, which has absorbed the inert gas, in the supply pipe from the inert gas absorption device to the guide contact downstream polymerization device to a pressure of 15 kPaA to 200 kPaA. <Condition (1)> The guide contact flow polymerization apparatus includes: a liquid receiving port; a liquid supply area for supplying liquid to the guides in the evaporation zone through a perforated plate; and an evaporation zone having a plurality of guides extending downward from the perforated plate within a space surrounded by the perforated plate, a side shell, and a bottom shell. A vacuum exhaust port is provided in the evaporation zone; And a liquid outlet, wherein the liquid outlet is located at the lowest part of the bottom housing; <Condition (2)> A flow path control component is provided in the liquid supply area, and the flow path control component has the function of causing the liquid supplied from the liquid receiving port to the perforated plate to flow from the periphery of the perforated plate to the center in the liquid supply area. <Condition (3)> The internal cross-sectional area A(m²) on the horizontal plane of the side shell of the evaporation zone 2 ) satisfies the following equation (I): 0.7≤A≤300 Formula (I); <Condition (4)> The internal cross-sectional area A (m 2 The internal cross-sectional area B (m²) on the horizontal plane of the liquid outlet 2 The ratio of ) satisfies the following equation (II): Equation (II): 20 ≤ A / B ≤ 1000; <Condition (5)> The bottom shell constituting the bottom of the evaporation zone is connected to the upper side shell inside the evaporation zone at an angle C degrees (°), and the angle C degrees satisfies the following formula (III): 110≤C≤165 Equation (III); <Condition (6)> The length h (cm) of the guide element satisfies equation (IV): Equation (IV): 150≤h≤5000; <Condition (7)> The total external surface area S(m²) of the plurality of guide elements 2 Satisfying equation (V): Equation (V) is given by equation (V) where 2 ≤ S ≤ 50000. <Condition (8)> per 1m 2 The average number of holes N (holes / m) in the perforated plate 2 ) satisfies the following formula (VI): Equation (VI): 50≤N≤3000; <Condition (9)> The upper area T(m²) of the porous plate, including the upper area of ​​the holes in the porous plate. 2 The sum of Q(m) and the effective cross-sectional area of ​​the hole 2 The ratio of ) satisfies the following equation (VII): 50≤T / Q≤3000 Equation (VII).

70. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69, wherein, The angle E (°) formed between the inner sidewall of the liquid supply zone and the perforated plate satisfies the following formula (VIII): 100≤E<180 Equation (VIII).

71. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, The distance K (cm) between the guide member and the inner wall surface of the side shell closest to the evaporation zone satisfies the following formula (IX): Equation (IX) is given by 5≤K≤50.

72. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, The side shell of the evaporation zone is cylindrical with an inner diameter D (cm) and a length L (cm). The bottom shell connected to the lower part of the side shell is conical. The liquid outlet at the bottom of the conical bottom shell is cylindrical with an inner diameter d (cm). The terms D, L, and d satisfy the following equations (X), (XI), (XII), and (XIII): Equation (X) is given by equation (X) with a minimum value of 100 ≤ D ≤ 1800. 5≤D / d≤50 Equation (XI) 0.5≤L / D≤30 Formula (XII) h-20≤L≤h+300 Formula (XIII) In formula (XIII), h (cm) represents the length of the guide.

73. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, The volume V(m³) of liquid that can exist in the liquid supply area from the liquid inlet to the upper surface of the perforated plate. 3 The upper area T(m²) of the porous plate containing the holes of the porous plate. 2 ) satisfies the following equation (XIV): 0.02(m)≤V / T≤0.5(m) Equation (XIV).

74. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, The liquid supply area has a spatial volume V(m) capable of holding liquid. 3 ) and the spatial volume Y (m) of the evaporation zone 3 The following equation must be satisfied: 10≤Y / V≤500.

75. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, At least one of the guides is a cylindrical guide with an outer diameter r (cm) or a tubular guide that prevents liquid and / or gaseous substances from entering the inside of the guide, and The outer diameter r satisfies the following formula (XV): 0.1≤r≤1 Equation (XV).

76. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, The guide contact downflow polymerization apparatus has a plurality of guides, and the plurality of guides are joined together using a support material.

77. The apparatus for manufacturing aromatic branched polycarbonate according to claim 69 or 70, wherein, The plurality of guides are selected from any one of the following groups: a grid-like or mesh-like guide obtained by fixing each guide with a lateral support material; a three-dimensional guide obtained by arranging a plurality of grid-like or mesh-like guides in front and behind and fixing these guides with a lateral support material; and a climbing frame-like three-dimensional guide obtained by fixing each of the plurality of guides in front, behind, left, and right with a lateral support material.

Images