TWI828098B - Method for producing polycarbonate - Google Patents

Abstract

The present invention aims to provide a novel method for producing polycarbonate. The method for producing polycarbonate includes a step of manufacturing polycarbonate by melt polycondensation, wherein a dihydroxy compound, a diaryl carbonate compound or a prepolymer thereof that serves as a source material flows along an external surface of a guide. The aforesaid dihydroxy compound contains a dihydroxy compound represented by Formula (1):

Description

How to make polycarbonate

The present invention relates to a manufacturing method of polycarbonate and polycarbonate.

As a method of producing polycarbonate, a method of producing polycarbonate derived from dihydroxy compounds and/or glycols derived from sugars such as isosorbide has been proposed (see, for example, Patent Documents 1 to 6).

[Prior technical literature]

[Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2006-36954

Patent Document 2: International Publication No. 2004/111106

Patent Document 3: International Publication No. 2008/093860

Patent Document 4: Japanese Patent Application Publication No. 2008-56844

Patent Document 5: Japanese Patent Application Publication No. 2013-209585

Patent Document 6: Japanese Patent Application Publication No. 2017-8140

Compounds having an isosorbide skeleton have attracted attention as natural resources. On the other hand, methods for producing polycarbonates using compounds having an isosorbide skeleton have been conventionally shown (for example, as shown in Patent Documents 1 to 6). method), a stirred tank polymerization device is used. However, when a compound having an isosorbide skeleton is dissolved, kneading is performed by applying a high shear force that results in a high melt viscosity, which causes the viscosity of the polycarbonate to increase, the haze to decrease, and the hue to deteriorate.

Therefore, an object of the present invention is to provide a method for producing a polycarbonate that uses a compound having an isosorbide skeleton and has low viscosity, low haze, and a better hue, and a polycarbonate.

That is, the present invention is explained as follows.

<1>

A method for manufacturing polycarbonate, which includes: using dihydroxy compounds and diaryl carbonate compounds or prepolymers thereof as raw materials, flowing down along the outer surface of a guide member, and manufacturing polycarbonate by a melt polycondensation method. ester step,

The aforementioned dihydroxy compound contains a dihydroxy compound represented by the following formula (1),

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and a cycloalkyl group with 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. .

<2>

The manufacturing method of polycarbonate as described in <1>, wherein the mass ratio of the dihydroxy compound represented by the formula (1) with respect to the total amount of the dihydroxy compound exceeds 0.98, and

The reaction temperature in the aforementioned melt polycondensation method exceeds 220°C and is 330°C or lower.

〈3〉

The manufacturing method of polycarbonate according to <1>, wherein the dihydroxy compound contains an aliphatic diol compound, an alicyclic diol compound and a bisphenol compound represented by the following formula (3). More than 1 species in a group,

HO-R ₅ -OH (3)

In the formula, R ₅ represents an alkylene group having 2 to 12 carbon atoms.

〈4〉

The manufacturing method of polycarbonate as described in <3>, wherein the mass ratio of the dihydroxy compound represented by the formula (1) is 0.5 or more and 0.98 or less with respect to the total amount of the dihydroxy compound, and

The reaction temperature in the aforementioned melt polycondensation method is 170 to 220°C.

〈5〉

The method for producing polycarbonate according to any one of <1> to <4>, wherein the diaryl carbonate compound contains a diaryl carbonate compound obtained using carbon dioxide as a raw material.

〈6〉

The method for producing polycarbonate according to any one of <1> to <5>, wherein the diaryl carbonate compound contains diphenyl carbonate.

〈7〉

The manufacturing method of polycarbonate according to any one of <1> to <6>, wherein the dihydroxy compound represented by the aforementioned formula (1) contains isosorbide (Isosorbide), isomannose One or more of the group consisting of Isomannide and Isoidide.

<8>

The manufacturing method of polycarbonate according to any one of <1> to <7>, wherein the dihydroxy compound represented by the aforementioned formula (1) contains a compound represented by the following formula (4),

<9>

The manufacturing method of polycarbonate according to any one of <1> to <8>, wherein the melt volume flow rate (MVR: Melt Volume Flow Rate) of the obtained polycarbonate is 1.5 at 270°C. to 75cm ³ /10min.

〈10〉

The method for producing polycarbonate according to any one of <1> to <9>, wherein the raw material is a raw material that has absorbed nitrogen.

〈11〉

The manufacturing method of polycarbonate according to <3>, wherein the aliphatic diol compound represented by the formula (3) contains a compound selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. , one or more from the group consisting of 1,5-pentanediol and 1,6-hexanediol,

The alicyclic diol compound contains one or more types selected from the group consisting of 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol.

〈12〉

The manufacturing method of polycarbonate according to any one of <1> to <11>, wherein the step of manufacturing the polycarbonate is performed using a guide contact flow polymerization device,

The aforementioned guide contact flow polymerization device satisfies the following <Condition (1)> to <Condition (9)>,

〈Condition (1)〉

It has: a liquid receiving port, a liquid supply area of a guide for supplying liquid to the evaporation area through the porous plate; a space surrounded by the aforementioned porous plate, the side shell and the bottom shell is provided with a downward direction from the aforementioned porous plate. An evaporation zone of a plurality of extending guides; a vacuum vent provided in the aforementioned evaporation zone; and a liquid discharge port provided at the lowermost part of the bottom housing;

〈Condition (2)〉

In the liquid supply area, a flow path control member is provided in the liquid supply area, and the flow path control member has a mechanism for allowing the liquid supplied from the liquid receiving port to the porous plate to flow from the peripheral part to the center part of the porous plate. The function of direction;

〈Condition (3)〉

The internal cross-sectional area A (m ² ) in the horizontal plane of the side shell of the aforementioned evaporation zone satisfies the following formula (I),

0.7≦A≦300 Formula (I)

〈Condition (4)〉

The ratio of the internal cross-sectional area A (m ² ) to the internal cross-sectional area B (m ² ) in the horizontal plane of the liquid discharge port satisfies the following formula (II),

20≦A/B≦1000 Formula (II)

〈Condition (5)〉

Relative to the upper side shell, the bottom shell constituting the bottom of the aforementioned evaporation zone is connected at an angle C degrees in the interior, and the aforementioned angle C degrees satisfies the following formula (III),

110≦C≦165 Formula (III)

〈Condition (6)〉

The length h (cm) of the aforementioned guide satisfies formula (IV),

150≦h≦5000 Formula (IV)

〈Condition (7)〉

The total external surface area S (m ² ) of the plurality of aforementioned guide members satisfies the formula (V),

2≦S≦50000 formula (V)

〈Condition (8)〉

The average number of holes N (pieces/m ² ) per 1 m ² of the aforementioned porous plate satisfies formula (VI),

50≦N≦3000 Formula (VI)

〈Condition (9)〉

The ratio of the upper area T (m ² ) of the aforementioned porous plate including the upper area of the holes of the aforementioned porous plate to the total effective cross-sectional area Q (m ² ) of the aforementioned holes satisfies the following formula (VII),

50≦T/Q≦3000 Formula (VII).

〈13〉

A polycarbonate having structural units represented by the following formula (2),

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and a cycloalkyl group with 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. .

〈14〉

The polycarbonate as described in <13>, wherein the mass ratio of the structural units represented by formula (2) relative to the total amount of polycarbonate exceeds 0.98.

〈15〉

The polycarbonate according to <13>, wherein the dihydroxy compound contains: a structural unit selected from an aliphatic diol compound represented by the following formula (5), a structure derived from an alicyclic diol compound One or more types from the group consisting of units and structural units derived from bisphenol compounds,

-OR ₅ -OC(O)- (5)

In the formula, R ₅ represents an alkylene group having 2 to 12 carbon atoms.

〈16〉

The polycarbonate as described in <15>, wherein the mass ratio of the structural units represented by formula (2) relative to the total amount of polycarbonate is 0.5 or more and 0.98 or less.

〈17〉

The polycarbonate according to any one of <13> to <16>, wherein the melt volume flow rate (MVR) is 40 cm ³ /10 min or less at 230°C.

〈18〉

The polycarbonate according to any one of <13> to <17>, wherein the melt volume flow rate (MVR) is 1.5 to 75 cm ³ /10min at 270°C.

〈19〉

The polycarbonate according to any one of <13> to <18>, wherein the haze is 0.8% or less.

〈20〉

The polycarbonate according to any one of <13> to <19>, wherein the b* value is 0.7 or less.

According to the present invention, it is possible to provide a method for producing a polycarbonate that uses a compound having an isosorbide skeleton and has low viscosity, low haze, and a better hue, and a polycarbonate.

1: Liquid receiving port

2:Porous plate

3: Liquid supply area

4: Guide

5: Evaporation zone belonging to internal space

6: Vacuum vent

7: Liquid discharge port

8: Discharge pump

9: Inert gas supply port

10:Side shell

11: Bottom shell

12: Take out the exit

15: Inert gas absorption zone belonging to the internal space

20:Flow path control component

21: The hole part of the multi-well plate

22: Internal side wall surface of liquid supply area

23: Upper internal wall of liquid supply area

31: Mixing tank

32,34A,34B: Transfer pump

33A, 33B: Dissolution mixture storage tank

35: 1st Aggregator

36,38,40,43,46A,46B,49A,49B: Supply pump

37: 2nd aggregator

39: The first inert gas absorption device

41,47A,47B: Pressure regulating valve

42: The first guide contacts the downflow polymerization device

44: The second inert gas absorption device

45:Three-way polymer valve

48A, 48B: Second guide contact flow polymerization device

50A: Rear section machine

50B: Rear section machine

a-a': section plane

b-b': horizontal plane

h: length of guide

L: length

D:polymer size

d:Inner diameter (pipe diameter)

r: outer diameter

E:Angle

FIG. 1 is a schematic structural diagram showing an example of an inert gas absorbing device constituting a polycarbonate manufacturing apparatus.

FIG. 2 is a schematic structural diagram showing an example of a guide contact flow polymerization apparatus constituting a polycarbonate manufacturing apparatus.

3 is a schematic diagram showing the upper part of an example of an inert gas absorbing device and a guide contact flow polymerization device.

4 is an enlarged schematic diagram showing the upper part of an example of an inert gas absorbing device and a guide contact flow polymerization device.

FIG. 5 is a schematic structural diagram showing an example of a polycarbonate manufacturing apparatus according to this embodiment.

The following is a detailed description of a mode for implementing the present invention (hereinafter also referred to as "this embodiment"). However, the present invention is not limited to this embodiment, and can be implemented with various modifications within the scope of the gist.

[Manufacturing method of polycarbonate]

The manufacturing method of polycarbonate in this embodiment includes: using dihydroxy compounds and diaryl carbonate compounds or prepolymers thereof as raw materials, flowing down along the outer surface of the guide member and using a melt polycondensation method. In the step of producing polycarbonate, the dihydroxy compound contains a dihydroxy compound represented by the following formula (1).

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and a cycloalkyl group with 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. .

According to this embodiment, it is possible to provide a method for producing a polycarbonate that uses a compound having an isosorbide skeleton and has low viscosity, low haze, and a better hue, and a polycarbonate.

According to this embodiment, the above-mentioned effect is achieved by making the raw material flow down along the outer surface of the guide and manufacturing polycarbonate by a melt polycondensation method. That is, the polycondensation of the dihydroxy compound and the diaryl carbonate compound is carried out by making the raw material flow down along the outer surface of the guide through the melt polycondensation method. Even if the raw material has a high viscosity after being melted, stirring is not required. The power enables aggregation.

The "guide" used in this embodiment means an object along which the raw material in a molten state moves. The guide member is not particularly limited, and examples thereof include pipes, rods, and the like.

〈Guide and guide contact flow type polymerization device〉

In the melt polymerization method, it flows down along the outer surface of the guide. The melt polymerization condensation method can use, for example, a guide contact flow type polymerization apparatus.

First, the polycarbonate manufacturing method of this embodiment is preferably to first manufacture a molten prepolymer in a stirred tank type polymerizer. Preferably, the obtained prepolymer is used as a raw material, and the prepolymer is further polymerized using a guide contact flow type polymerization device that performs polymerization while allowing the raw material to fall freely along the guide. The following description takes the case of using a prepolymer as a raw material as an example.

In the polycarbonate manufacturing method of this embodiment, the raw material is preferably a raw material that has absorbed nitrogen. That is, in the manufacturing method of polycarbonate of this embodiment, it is preferable to arrange|position so that an inert gas may be absorbed in the molten prepolymer of polycarbonate before being supplied to a guide contact flow type polymerization apparatus. Inert gas absorption device. In addition, in this embodiment, when a plurality of base guides are connected and used in contact with a downflow polymerization device, it is preferable to provide each polymerization device with an arrangement so that the inert gas is absorbed before being supplied to the polymerization device. Inert gas absorber for polycarbonate melt prepolymers. By providing the inert gas absorbing device, the effect of the present invention tends to be further improved. The inert gas absorption equipment is not particularly limited, and examples thereof include a vertical cylindrical tank (such as a vertical cylindrical tank) and a stirring tank with metal wires and/or metal mesh installed inside.

The manufacturing method is not particularly limited, and may refer to, for example, International Publication No. 1997/22650, International Publication No. 1999/36457, International Publication No. 2005/121211, International Publication No. 2005/123805, International Publication No. 2006/64656, International Publication No. 2006/64664, International Publication No. 2006/64667, International Publication No. 2006/67993, International Publication No. 2006/67994.

In the guide contact flow type polymerization device used in this embodiment, by causing the raw material to flow down along the outer surface of the guide, for example, the prepolymer of the raw material flows by its own weight. During this period, efficient surface renewal accompanied by natural stirring within the prepolymer is carried out, so the polymerization reaction can be carried out at a relatively low temperature. Therefore, the preferred reaction temperature is 100 to 280°C, more preferably 150 to 260°C. In this way, the manufacturing method of this embodiment allows the raw material to flow down along the outer surface of the guide, thereby enabling sufficient polymerization at low temperatures compared to the conventional mechanical stirring polymerizer. This is one of the reasons why high-quality polycarbonate can be produced without coloration or deterioration in physical properties.

The material of the guide contacting the downflow polymerization device or piping used in this embodiment is not particularly limited, and can be selected from, for example: stainless steel, carbon steel, Hastelloy, nickel, and titanium. , chromium and other alloys, or polymer materials with high heat resistance. In addition, the surface of these materials can be subjected to various treatments such as plating, lining, inert treatment, acid cleaning, phenol cleaning, etc. if necessary. Stainless steel or nickel, glass lining, etc. are preferred, and stainless steel is particularly preferred. The discharge pump for molten prepolymer or polycarbonate is preferably a gear pump that can discharge high-viscosity substances quantitatively. The material of these gears can be stainless steel or other special metals.

The melt polycondensation method is preferably performed under reduced pressure. Although it varies depending on the type, molecular weight, polymerization temperature, etc. of the polycarbonate to be produced, the number average molecular weight of the polycarbonate to be produced is within the range of 7,000 or less. , preferably in the range of 400 to 3,000 Pa. When the number average molecular weight of the polycarbonate produced is 7,000 to 15,000, preferably in the range of 50 to 500 Pa. When the number average molecular weight of the polycarbonate produced is 15,000 or more, it is preferably 300 Pa or less, and it is especially suitable to use the range of 20 to 250 Pa.

The reaction temperature in the melt polycondensation method may be, for example, 170°C to 330°C, preferably 170°C to 330°C, more preferably 170°C to 330°C.

〈Raw materials used in the manufacturing method of polycarbonate〉

In the polycarbonate manufacturing method of this embodiment, a dihydroxy compound and a diaryl carbonate compound or a prepolymer thereof are used as raw materials.

The following is a description of the dihydroxy compound and the diaryl carbonate compound as raw materials used in the method for producing polycarbonate according to this embodiment.

(dihydroxy compound)

The dihydroxy compound used in the polycarbonate manufacturing method of this embodiment contains at least a dihydroxy compound represented by the following formula (1).

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group having 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. .

The dihydroxy compound represented by the above formula (1) preferably contains one or more types selected from the group consisting of isosorbide, isomannitol and isoidide. These isosorbide, isomannitol, and isoidide are in the relationship of stereoisomers.

The dihydroxy compound represented by the above formula (1) preferably contains a compound represented by the following formula (4).

In the formula (4), the dotted line and the thick line represent the positional relationship of the trans form, and the dotted lines represent the positional relationship of the cis form.

These dihydroxy compounds can be used individually by 1 type or in combination of 2 or more types.

Among these dihydroxy compounds, isosorbide obtained by dehydration condensation of sorbitol (Sorbitol), which is produced from various starches that are abundantly available as a resource derived from plants and is easily available, has great advantages in terms of ease of acquisition and production, It is particularly good in terms of colorability, thermal stability, and mechanical properties.

In the manufacturing method of polycarbonate of this embodiment, it is preferable to contain an aliphatic diol compound represented by the following formula (3), an alicyclic diol compound, and a bisphenol compound selected from the group. One or more of them are used as dihydroxy compounds.

HO-R ₅ -OH (3)

In the formula, R ₅ represents an alkylene group having 2 to 12 carbon atoms.

The aliphatic diol compound represented by formula (3) is preferably selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol More than 1 species.

The alicyclic diol compound is preferably selected from 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol. One or more kinds, more preferably one or more kinds selected from the group consisting of 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, particularly preferably 1,4-cyclohexanediol. Methanol. 1,4-Cyclohexane dimethanol has cis and trans isomers. It can be a mixture of cis and trans. The mixing ratio (mass ratio) is not particularly limited and can be easily obtained. A mixing ratio of 40/60 to 70/30.

The bisphenol compound is not particularly limited, but is preferably selected from, for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A), 1,1-bis(4-hydroxyphenyl)-1-benzene ethane (bisphenol-AP), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol-AF), 2,2-bis(4-hydroxyphenyl)butane (bisphenol- B), bis(4-hydroxyphenyl)diphenylmethane (bisphenol-BP), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol-C), 1,1 -Bis(4-hydroxyphenyl)ethane (bisphenol-E), bis(4-hydroxyphenyl)methane (bisphenol-F), 5,5'-(1-methylethylene)-bis One or more types of [1,1'-(diphenyl)-2-ol]propane (bisphenol-PH), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol-Z), Particularly preferred is bisphenol-A.

The dihydroxy compound used in this embodiment may be one type alone or two or more types.

A trivalent trihydroxy compound for introducing a branched structure may also be used together.

(diaryl carbonate compound)

The diaryl carbonate compound used in this embodiment is preferably a diaryl carbonate compound represented by the following formula (A).

In the formula, Ar ³ and Ar ⁴ each independently represent a monovalent aromatic group having 5 to 20 carbon atoms.

Ar ³ and Ar ⁴ are preferably monovalent carbocyclic or heterocyclic aromatic groups. In Ar ³ and Ar ⁴ , one or more hydrogen atoms may be substituted by other substituents that do not adversely affect the reaction, such as halogen atoms, alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. Substituted with oxygen group, phenyl group, phenoxy group, vinyl group, cyano group, ester group, amide group, nitro group, etc. Ar ³ and Ar ⁴ may be the same or different. Representative examples of the monovalent aromatic groups Ar ³ and Ar ⁴ are not particularly limited, and examples thereof include phenyl, naphthyl, biphenyl, and pyridyl. These may be substituted by one or more of the above substituents. Preferred Ar ³ and Ar ⁴ are not particularly limited, and examples thereof include those represented by the following formulas.

Representative examples of the diaryl carbonate compound are not particularly limited, and examples thereof include substituted or unsubstituted diphenyl carbonates represented by the following formula (A-1).

In the formula, R ⁹ and R ¹⁰ each independently represent a hydrogen 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 carbon atoms in the ring, or a phenyl group, p and q are each independently an integer from 1 to 5. When p is 2 or more, each R ⁹ may be a different one. When q is 2 or more, each R ¹⁰ may be a different one.

Among the diaryl carbonate compounds, preferred are unsubstituted diphenyl carbonate, or symmetrical carbonic acids such as xylyl carbonate, lower alkyl-substituted diphenyl carbonate such as di(tert-butyl)phenyl carbonate. Diaryl esters. Particularly suitable is diphenyl carbonate, which is a diaryl carbonate of simple structure. These diaryl carbonate compounds can be used alone or in combination of two or more types.

Furthermore, the diaryl carbonate compound preferably contains a diaryl carbonate compound obtained using carbon dioxide as a raw material.

As the diaryl carbonate compound used as a raw material in the production method of this embodiment, a particularly preferred one is ethyl carbonate produced/purified by reacting ethylene oxide with _CO2 , and then the ethyl carbonate is The dimethyl carbonate is produced/refined by reacting with methanol, and then the dimethyl carbonate and the purified phenol are produced/refined by reactive distillation. The diphenyl carbonate is free of alkali metals/alkaline earth metals and Ultra-high purity chlorine. The manufacturing method is not particularly limited, and may refer to, for example, International Publication No. 2004/105696, International Publication No. 2007/34669, International Publication No. 2007/60893, International Publication No. 2007/60984, International Publication No. Publication No. 2007/69462, International Publication No. 2007/69513, International Publication No. 2007/69514, International Publication No. 2007/72728, International Publication No. 2005/123638, International Publication No. 2007/74692 International Publication No. 2007/88782, International Publication No. 2006/1256, International Publication No. 2006/1257, International Publication No. 2006/6566, International Publication No. 2006/6568, International Publication No. International Publication No. 2006/6585, International Publication No. 2006/6588, International Publication No. 2006/41075, International Publication No. 2006/43491, International Publication No. 2007/69529, International Publication No. 2007/69531 Gazette, International Publication No. 2007/72705, etc. Furthermore, suitable examples of the diaryl carbonate compound used as a raw material in the production method of this embodiment include dialkyl carbonate produced/purified by reacting alcohol with _CO2 , and then the dialkyl carbonate is Diphenyl carbonate is produced/purified by reacting with purified phenol. The manufacturing method is not particularly limited, and may refer to, for example, International Publication No. 2005/783, International Publication No. 2007/114130, International Publication No. 2003/55840, International Publication No. 2011/105442, International Publication No. Publication of Gazette No. 2006/67982, etc.

(melt prepolymer)

The molten prepolymer of the raw material used in the method for producing polycarbonate according to this embodiment is produced from the aforementioned dihydroxy compound and diaryl carbonate. This usage ratio (input ratio) varies depending on the types of the dihydroxy compound and diaryl carbonate compound used, the polymerization temperature, and other polymerization conditions. However, for 1 mole of the dihydroxy compound, the diaryl carbonate compound It is usually used in a ratio of 0.9 to 2.5 mol, preferably 0.95 to 2.0 mol, and more preferably 0.98 to 1.5 mol.

The prepolymer in a molten state (melt prepolymer) produced from the aforementioned dihydroxy compound and diaryl carbonate compound means that it is compared to the purposeful polymerization produced from the dihydroxy compound and diaryl carbonate compound. Of course, the melt in the middle of polymerization of polycarbonate with a lower degree of polymerization can also be an oligomer.

The average degree of polymerization of the molten prepolymer of polycarbonate that can be produced by the polycarbonate production method of this embodiment can be arbitrary. In addition, although it differs depending on the chemical structure, it is usually about 2 to 2,000.

Such a molten prepolymer used as a polymerization raw material can be obtained by any conventional method.

In this embodiment, the molar ratio of the total number of dihydroxy compounds to the diaryl carbonate compound, that is, the input molar ratio, is determined by the number average molecular weight Mn or OH% of the intended polycarbonate, and the molar ratio of the dihydroxy compound. The total amount is determined by the type of diaryl carbonate, polymerization temperature and other polymerization conditions. From the viewpoint of achieving a better polymerization reaction and more effectively preventing coloration or decrease in heat resistance, the input ratio within the predetermined range is the input amount of the diaryl carbonate compound relative to the total input amount of the dihydroxy compound, so as to On a molar basis, 0.90 to 1.15 is preferred, 0.92 to 1.13 is more preferred, and 0.94 to 1.10 is more preferred.

(catalyst)

Although the reaction of producing polycarbonate from a dihydroxy compound and a diaryl carbonate compound can be carried out without adding a catalyst, in order to increase the polymerization speed, it can also be carried out in the presence of a catalyst if necessary.

There are no special restrictions on the catalyst as long as it is used in the field.

The catalyst used in this embodiment is not particularly limited, and examples thereof include alkali metal or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; lithium aluminum hydride, Alkali metal salts, alkaline earth metal salts, and quaternary ammonium salts of boron or aluminum hydrides such as sodium boron hydride and tetramethylammonium boron hydride; alkali metal or alkaline earth metal hydrides such as lithium hydride, sodium hydride, calcium hydride, etc.; Lithium methoxide, sodium ethoxide, calcium methoxide and other alkali metal or alkaline earth metal alkoxides; lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO-Ar-OLi, NaO-Ar-ONa (Ar is aromatic Aromatic oxides of alkali metals or alkaline earth metals such as base); organic acid salts of alkali metals or alkaline earth metals such as lithium acetate, calcium acetate, sodium benzoate; zinc compounds such as zinc oxide, zinc acetate, zinc phenoxide, etc.; boron oxide , boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate and other boron compounds and other catalysts. The catalyst can be used alone or in combination of two or more types.

Among them, hydroxides of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide are preferred.

In addition, from the viewpoint of achieving a practically good polymerization reaction and preventing coloration or reduction in heat resistance, the amount of the catalyst used is preferably 50 to 1,000 ppb, more preferably 60 to 60 ppb, based on the diaryl carbonate compound as the raw material. 500ppb, and preferably 70 to 250ppb.

In this embodiment, colorants, heat-resistant stabilizers, antioxidants, weather-resistant agents, ultraviolet absorbers, release agents, lubricants, antistatic agents, plasticizers, etc. may also be added and used as needed. In addition, these additives can be added when the polycarbonate is in a molten state after the polymerization is completed, or the additives can be added after the polycarbonate is granulated and melt-kneaded again.

The ratio of hydroxyl group to aryl carbonate group is not particularly limited, but is preferably in the range of 95:5 to 5:95, more preferably in the range of 90:10 to 10:90, and still more preferably in the range of 80:20 to 20:80 range. Particularly preferred ones are polycarbonates in which the ratio of phenyl carbonate groups in the terminal groups is 85 mol% or more.

In addition, the production device used in the polycarbonate production method of this embodiment may be a combination of a plurality of the above-mentioned guide contact flow polymerization devices, or may be additionally equipped with devices and equipment having any other functions other than polymerization.

In the manufacturing method of polycarbonate of this embodiment, although there is no particular limitation, a conventional catalyst deactivator described in International Publication No. 2005/121213 may be used.

The dosage of the catalyst deactivator is preferably a ratio of 0.5 to 50 moles per 1 mole of transesterification catalyst, more preferably a ratio of 0.5 to 10 moles, and still more preferably a ratio of 0.8 to 5 moles. . The catalyst deactivator is added, for example, in the extruder.

In the method for producing polycarbonate of this embodiment, the mass ratio of the dihydroxy compound represented by the formula (1) relative to the total amount of the dihydroxy compound is preferably more than 0.98, and the reaction temperature in the melt polycondensation method Preferably, the temperature exceeds 220°C and is not more than 330°C (hereinafter, this embodiment is also referred to as "manufacturing method (1)"). That is, when the ratio of the dihydroxy compound of formula (1) is high, the viscosity during melting will increase, so polymerization cannot be performed in a stirred tank type polymerization device. However, polymerization can be performed by using the above-mentioned melt polymerization condensation method. .

In the production method (1), the mass ratio of the dihydroxy compound represented by the formula (1) relative to the total amount of the dihydroxy compound may be 0.99 or more, or may be 1.00.

In the production method (1), the reaction temperature is preferably more than 220°C and 330°C or less.

In the method for producing polycarbonate of this embodiment, the mass ratio of the dihydroxy compound represented by formula (1) relative to the total amount of the dihydroxy compound is preferably 0.5 or more and 0.98 or less, and in the melt polycondensation method The reaction temperature is preferably 170 to 220°C (hereinafter, this embodiment is also referred to as "manufacturing method (2)"). In the polymerization method performed by a stirred tank type polymerization apparatus, polymerization is performed by reducing the mass ratio of the dihydroxy compound represented by formula (1) in order to reduce the viscosity during melting, but the polymerization must be performed at a high temperature. In contrast, by using the melt polycondensation method, polymerization can be performed at low temperatures.

In the production method (2), the mass ratio of the dihydroxy compound represented by the formula (1) to the total amount of the dihydroxy compound may be 0.55 or more and 0.90 or less, or may be 0.65 or more and 0.85 or less.

In the production method (2), from the viewpoint of reducing the viscosity during melting, the dihydroxy compound preferably contains an aliphatic diol compound represented by the above formula (3). Relative to dihydroxy compounds The mass ratio of the aliphatic diol compound represented by the formula (3) is preferably 0.02 or more and 0.5 or less, more preferably 0.02 or more and 0.4 or less, based on the total amount of substances, and still more preferably 0.02 or more and 0.3 or less.

In the manufacturing method of this embodiment, the melt volume flow rate (MVR) of the polycarbonate obtained is preferably 1.5 to 75 cm ³ /10min at 270°C. Even polycarbonate with such a melt viscosity can be polymerized by the melt polycondensation method to produce polycarbonate with low viscosity, low haze and better hue. The MVR can be 1.5 to 20cm ³ /10min at 270°C, or 1.5 to 15cm ³ /10min, or 1.5 to 10cm ³ /10min. That is, even when the content ratio of isosorbide is high and the melt viscosity is low, that is, when a raw material is used whose mass ratio of the dihydroxy compound represented by the formula (1) is 0.99 or more relative to the total amount of the dihydroxy compound. , it can also produce polycarbonate with low viscosity, low haze and better hue.

In addition, from another point of view, the MVR at 270°C is preferably 5 to 60cm ³ /10min, more preferably 10 to 50cm ³ /10min, and still more preferably 20 to 45cm ³ /10min. In making polycarbonates that thus exhibit MVR, the reaction temperature can be lowered. The MVR can be adjusted by reducing the content ratio of the dihydroxy compound represented by formula (1) in the total amount of dihydroxy compounds.

The manufacturing method of this embodiment may be a continuous manufacturing method. The so-called continuous manufacturing method is a method of continuously manufacturing polycarbonate without interruption. The polycarbonate output of the manufacturing method of this embodiment may be, for example, 10 kg/h or more, 20 kg/h, or 1 ton/h.

The details of the polycarbonate manufacturing method of this embodiment will be described in order below.

[Manufacturing equipment used in the manufacturing method of polycarbonate]

Hereinafter, an example of the specific structure of the polycarbonate manufacturing apparatus used in the polycarbonate manufacturing method of this embodiment is demonstrated with reference to a drawing.

FIG. 5 is a schematic block diagram showing an example of a polycarbonate manufacturing apparatus used in this embodiment. In this polycarbonate manufacturing apparatus, the polymerization raw materials and catalyst are put into the mixing tank 31 and mixed, and then transported to the dissolved mixture storage tanks 33A and 33B by the transfer pump 32, and then further transferred from there by the transfer pump 34A. , 34B is transported, and pre-polymerized in the first polymerizer 35.

Furthermore, prepolymerization is performed in the second polymerizer 37 via the discharge gear pump 36 to obtain a polycarbonate prepolymer.

The polycarbonate prepolymer is transported to the first inert gas absorption device 39 through the supply pump 38, and the solubility of the inert gas is adjusted by the pressure adjustment valve 41, and then transported to the first guide contact flow polymerization device 42. Perform aggregation. Here, the phenol is discharged from the vent as a low molecular weight component that is a low boiling point substance.

Then, it is transported to the second inert gas absorbing device 44 via the supply pump 43, and then transported from there by the supply pumps 46A and 46B. The solubility of the inert gas is adjusted by the pressure adjustment valves 47A and 47B, and is sent to the connected second guide contact flow polymerization devices 48A and 48B for polymerization. Here, phenol is discharged from the vent.

Then, it is transported by supply pumps 49A and 49B, and additives are added to the subsequent machines 50A and 50B to obtain the desired polycarbonate.

The types of the pressure regulating valves 41, 47A, and 47B for adjusting the solubility of the inert gas are not limited. They may be valves installed in predetermined pipes or other machines capable of controlling a predetermined pressure.

In the polycarbonate manufacturing method of this embodiment, it is preferable to use a guide contact flow polymerization device to evaporate low-boiling-point substances. In addition, the guide contact flow polymerization device preferably satisfies <Condition (1)> to <Condition (9)> described below.

FIG. 1 is a schematic configuration diagram showing an example of the inert gas absorbing devices 39 and 44, and FIG. 2 is a schematic configuration diagram showing an example of the guide contact flow polymerization devices 42, 48A, and 48B. The inert gas absorption device shown in Figure 1 and the guide contact flow device shown in Figure 2 have an inert gas absorption zone for absorbing inert gas and an evaporation zone for evaporating low-boiling point substances in their respective internal spaces. They are different from each other, but the basic device structure is the same.

3 and 4 are upper schematic diagrams showing an example of an inert gas absorbing device and a guide contact type downflow polymerization device.

In the polycarbonate manufacturing apparatus used in this embodiment, the guide contact flow polymerization apparatus preferably satisfies the following <Condition (1)> to <Condition (9)>.

〈Condition (1)〉

It has: a liquid receiving port 1, a liquid supply area 3 of a guide 4 for supplying liquid to the evaporation area 5 through the porous plate 2; in the space surrounded by the aforementioned porous plate 2, the side shell 10 and the bottom shell 11 An evaporation zone 3 is provided with a plurality of guides 4 extending downward from the porous plate 2; a vacuum vent 6 is provided in the evaporation zone 3; and a liquid discharge port 7 is provided at the lowest part of the bottom shell.

〈Condition (2)〉

In the liquid supply area 3, a flow path control member 20 is provided in the liquid supply area 3, and the flow path control member 20 has: the liquid supplied from the liquid receiving port 1 to the porous plate 2, from the liquid receiving port 1 to the porous plate 2. The function of flowing from the peripheral part to the central part.

〈Condition (3)〉

The internal cross-sectional area A (m 2 ) in the horizontal plane of the side shell 10 of the evaporation zone 5 (the cross-sectional plane a-a' in Figure ² ) satisfies the following formula (I).

0.7≦A≦300 Formula (I)

〈Condition (4)〉

The ratio of the internal cross-sectional area A (m ² ) to the internal cross-sectional area B (m 2 ) in the horizontal plane of the liquid discharge port 7 (plane bb' in FIG. ² ) satisfies the formula (II).

20≦A/B≦1000 Formula (II)

By satisfying the aforementioned formula (II), there is a tendency to discharge the molten material with an increased melt viscosity without deteriorating the quality of the liquid or polymer concentrated by evaporation or the polymer produced.

〈Condition (5)〉

Relative to the upper side shell 10, the bottom shell 11 constituting the bottom of the evaporation zone 5 is connected in the interior at an angle C, and the angle C preferably satisfies formula (III).

110≦C≦165 Formula (III)

In order to reduce the equipment cost, C is preferably as close to 90 degrees as possible, but in order to increase the melt viscosity without reducing the quality of the concentrated liquid or polymer falling from the lower end of the guide 4. When the melt moves to the discharge port 7, C preferably satisfies formula (III).

〈Condition (6)〉

The length h (cm) of the guide 4 satisfies the formula (IV).

150≦h≦5000 Formula (IV)

By setting the length h of the guide 4 to 150 cm or more, concentration or polymerization can be performed at a speed and quality sufficient for practical purposes. By setting h below 5000cm, the upper part of guide 4 and The difference in viscosity of the liquid in the lower part does not become too large, and it is possible to prevent changes in the degree of concentration or the degree of polymerization from occurring.

〈Condition (7)〉

The total external surface area S (m ² ) of the plurality of guides 4 satisfies the following formula (V).

2≦S≦50000 formula (V)

By setting S (m ² ) to 2 or more, the amount of evaporated liquid per hour or more and the throughput of polymer production tend to be achieved.

In addition, by setting S (m ² ) to be 50,000 or less, it is possible to reduce equipment costs, achieve this throughput, and eliminate variations in physical properties.

〈Condition (8)〉

The average number of holes N (pieces/m ² ) per 1 m ² of the aforementioned porous plate satisfies the formula (VI).

50≦N≦3000 Formula (VI)

The average number of holes N (number/m ² ) of the porous plate is a value obtained by dividing the total number of holes by the area of the upper surface of the porous plate 2 (the upper area including the holes) T (m ² ).

The holes of the porous plate 2 are preferably arranged almost uniformly on the porous plate 2, but because the distance K (cm) between the peripheral part of the porous plate 2 and the inner wall surface of the evaporation zone 5 is usually better than the distance between adjacent holes. The distance is longer, so the number of holes per unit area in the peripheral part is preferably less than the number of holes in the central part. In this embodiment, the average number of holes N is used in this sense. The better range of N is 70≦N≦2000, and the better range is 100≦N≦1000.

〈Condition (9)〉

The ratio of the upper area T (m ² ) of the porous plate including the upper area of the holes of the porous plate to the total effective cross-sectional area Q (m ² ) of the holes satisfies the following formula (VII).

50≦T/Q≦3000 Formula (VII)

The aforementioned T/Q is more preferably 100 to 2,500, and more preferably 250 to 1,500.

The so-called "effective cross-sectional area" of the holes of the porous plate refers to the area of the narrowest part of the cross-section of the hole through which the liquid passes. When the guide member 4 penetrates the hole, the area is the area obtained by subtracting the cross-sectional area of the guide member 4 from the cross-sectional area of the hole.

Q(m ² ) represents the total effective cross-sectional area of those holes.

When the aforementioned formulas (VI) and (VII) are satisfied, a large amount of liquid, especially a liquid with high viscosity, tends to be evaporated continuously and stably for a long time.

By using a polycarbonate manufacturing device that satisfies the above-mentioned constitution, not only the problems of conventional evaporation devices are solved, but also a colorless, high-quality and high-performance concentrated liquid or polymer tends to be obtained. In addition, by using the above-mentioned production device, it is possible to stably produce the evaporated liquid at an amount of 1 ton or more per hour and for a long time of more than thousands of hours, for example, more than 5,000 hours. .

In addition to the various reasons mentioned above, it is also presumed that the polycarbonate manufacturing apparatus satisfying the above configuration has such excellent effects because it exhibits a composite effect brought about by combining these conditions.

For example, a guide with a high surface area that satisfies the aforementioned formulas (IV) and (V) is extremely effective for efficient internal stirring and surface renewal of a large amount of liquid or prepolymer or polymer supplied at a relatively low temperature. , this can be inferred as: low-boiling point substances can be evaporated efficiently, which is beneficial to obtain high-quality concentrated liquid or polymer in a huge amount of more than 1 ton per hour, and satisfies the angle of the aforementioned formula (III) C can shorten the time until a large amount of high-quality concentrated liquid or polymer dropped from the guide 4 is discharged from the liquid discharge port 7, thereby reducing heat history.

The performance of the guide contact flow polymerization device on an industrial scale can first be established by using large-scale manufacturing equipment for long periods of time. However, the cost of the manufacturing equipment at this time is also an important factor that should be considered.

The guide contact flow-type polymerization device constituting the above-mentioned polycarbonate manufacturing device can reduce equipment costs relative to performance compared with conventional evaporation devices or polymerizers.

The specific conditions or suitable ranges of dimensions, angles, etc. of the above-mentioned guide contact flow-down polymerization device are as explained above, but the more preferable ranges are as explained below.

A better range of the internal cross-sectional area A (m ² ) in the horizontal plane of the side shell 10 of the evaporation zone 5 shown in formula (I) is 0.8≦A≦250, and a better range is 1≦A≦200.

In addition, a more preferable range of the ratio of the internal cross-sectional area A (m ² ) shown in the formula (II) to the internal cross-sectional area B (m ² ) in the horizontal plane of the liquid discharge port 7 is 25≦A/B≦900, and Better is 30≦A/B≦800.

In addition, a better range of the angle C formed by the bottom shell 11 that constitutes the bottom of the evaporation zone 5 and the upper side shell 10 in the interior is 120≦C≦165, and More preferably, it is 135≦C≦165. When using multiple guides to contact the downflow polymerization device to sequentially increase the concentration or polymerization degree, set the corresponding angles to C1, C2, C3. ． ． When , it is preferable that C1≦C2≦C3≦. ． ． .

In addition, the necessary length h (cm) of the guide 4 shown in formula (IV) depends 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, and the necessary concentration. Factors such as degree or degree of polymerization vary, but the preferred range is 200≦h≦3000, and the preferred range is 400<h≦2500.

In addition, the necessary total external surface area S (m ² ) of the entire guide shown in formula (V) also varies due to the same factors as above, but the optimal range is 10≦S≦40000, and more The best value is 15≦S≦30000.

In this specification, the total external surface area of the entire guide means the entire surface area of the guide where the liquid comes into contact and flows down. For example, in the case of a guide such as a pipe, it means the outer surface area and does not include the surface area where the liquid does not flow down. The surface area of the inside side of the tube.

As shown in FIGS. 1 to 3 , the liquid receiving port 1 is preferably located at the upper part of the liquid supply area 3 .

The liquid receiving port 1 can be one or a plurality of places. It is preferably arranged in such a way that the liquid is supplied to the porous plate 2 as uniformly as possible in the liquid supply area 3. In the case of one place, it is preferably arranged in The central part of the upper part of the liquid supply area 3.

In the liquid supply area 3, a flow path control member 20 having a function of causing the flow of the liquid supplied from the liquid receiving port 1 to the porous plate 2 to flow mainly from the peripheral part to the central part of the porous plate 2 is preferably provided. In the aforementioned liquid supply area 3. The flow path control member 20 has a hole portion (for example, 21) and an inner side wall surface 22 of the liquid supply area to prevent the liquid from remaining in the porous plate 2 for a long time by directing the flow of the liquid from the peripheral portion to the center of the porous plate 2. The effect of the space between. The liquid that mainly flows from the peripheral portion toward the central portion of the porous plate 2 is supplied to the guide 4 from the holes of the porous plate present therebetween.

The flow path control member 20 may have any shape as long as it can exert its effect. The cross-sectional shape is preferably similar to the cross-sectional shape of the porous plate 2 . The cross section of the flow path control member 20 here refers to a place showing the largest area when the flow path control member 20 is cut in a transverse plane.

Although the preferred range of the distance between the aforementioned flow path control member 20 and the inner side wall surface 22 of the liquid supply area 3 varies depending on the amount, viscosity, etc. of the liquid to be processed, it is only necessary when constituting the above-mentioned polycarbonate manufacturing device. When the guide member contacts a downflow polymerization device or an inert gas absorption device, and the viscosity of the liquid being processed is relatively high, it is usually preferably in the range of 1cm to 50cm, more preferably 2cm to 30cm, and even better 3cm to 20cm.

As shown in Figures 3 and 4, there is a predetermined interval between the upper inner wall 23 of the liquid supply area 3 and the flow path control member 20. This interval can be any, but it is preferably to minimize the amount of space in the liquid supply area 3. the residence time of the liquid. In this sense, the interval is preferably 1 cm to 200 cm, more preferably 2 cm to 170 cm, and still more preferably 3 cm to 150 cm.

The distance between the upper inner wall surface 23 of the liquid supply area 3 and the flow path control member 20 can be configured to be almost the same as the distance between the flow path control members 20 from the liquid receiving port 1 to the inner side wall surface 22 of the liquid supply area 3 , the flow path control member 20 may also be configured to gradually narrow the interval or gradually expand the interval.

In addition, the distance between the flow path control member 20 and the porous plate 2 is usually 1 cm to 50 cm, preferably 2 cm to 30 cm, and more preferably 3 cm to 20 cm.

The distance between the porous plate 2 and the flow path control member 20 may be almost the same as the distance from the inner side wall surface 22 of the liquid supply area 3 to the center of the porous plate, or may be configured to gradually narrow the distance, or is to gradually expand the interval. It is preferable to configure the flow path control member 20 with almost the same interval or with the interval gradually narrowed.

In order to prevent the liquid supplied from the liquid receiving port 1 from being directly introduced into the holes of the porous plate 2, the flow path control member 20 has a certain baffle function. When the area of the porous plate 2 is large, it is preferable that part of the supplied liquid does not pass through the peripheral part of the porous plate 2. Instead, it is short-circuited to the vicinity of the center of the porous plate 2. Therefore, it is also preferable to provide more than one hole near the center of the flow path control member 20 or other appropriate parts.

In order not to create an "ineffective area" in the liquid supply area 3, moreover, the angle formed by the internal side wall surface 22 of the liquid supply area and the porous plate 2, that is, E degree, preferably satisfies the following formula (VIII):

100≦E<180 Formula (VIII)

Here, when the inner side wall surface 22 of the liquid supply area is flat, in a cross-sectional plane perpendicular to the plane and perpendicular to the upper surface of the porous plate 2, the distance between the inner side wall surface 22 and the porous plate 2 is The angle formed is E.

In addition, when the internal side wall surface 22 is a concave curved surface, the tangent line at the point where the formed curve starts to rise in the cross-sectional plane perpendicular to the concave surface and perpendicular to the upper surface of the porous plate 2 is the same as that of the porous plate. The angle formed by the upper surface of 2 is E.

A better range of E is 120≦E<180, and a better range is 145≦E<180.

In addition, in the vicinity of the joint between the upper inner wall 23 and the inner wall 22 of the liquid supply area 3, it is better to avoid creating an "invalid area" by setting the angle formed by these two surfaces to be greater than 90°. , or when it is 90° or close to 90°, it is preferable to form a concave shape near the joint so that liquid does not remain.

In the above-mentioned polycarbonate manufacturing apparatus, the distance K (cm) between the guide 4 and the inner wall surface of the side housing 10 closest to the evaporation zone 5 preferably satisfies the following formula (IX).

5≦K≦50 formula (IX)

When the liquid adheres to the inner wall surface of the side shell 10 of the evaporation zone 5, evaporation and concentration will occur on the inner wall surface, causing the concentrated liquid to flow down along the inner wall surface. However, in order to maintain the heat preservation and/or heating of the evaporation zone 5, the inner wall usually uses water vapor or heat medium to heat the outer wall surface through a sheath, etc., or heats the outer wall surface through an electric heater, etc., so it is relatively Compared with the liquid flowing down the guide 4, the liquid adhering to the inner wall surface is highly concentrated and usually has a higher viscosity. In this way, the liquid with higher viscosity takes longer to flow down the wall (residence time), further forming a high viscosity.

And it is usually continuously heated from the outer wall surface, so it is also easy to cause thermal denaturation. Especially when used as a polymerizer or a polymer purification and/or recovery device, this tendency becomes extremely obvious when processing highly viscous liquids such as prepolymers and polymers. In this case, the polymer adhered to the inner wall surface of the evaporation zone 5 is likely to cause coloring, high molecular weight, and gelation. When such denatured substances are mixed, the polymer is not suitable as a product. Therefore, the distance K (cm) between the guide 4 closest to the inner wall and the inner wall should be long. However, in the case of industrial installations, if there are manufacturing cost considerations or if you want to use the smallest possible device to obtain high evaporation capacity time, it should be short.

By using the above-mentioned polycarbonate manufacturing equipment, adverse effects on the above-mentioned products can be suppressed, and the range of K (cm) can be set as short as possible (the aforementioned formula (IX)), so that it can be produced with a smaller device. High evaporation capacity is obtained.

From this point of view, a more preferable range of K (cm) is 10≦K≦40, and a more preferable range is 12≦K≦30.

In the above-mentioned polycarbonate manufacturing apparatus, the shape of the internal cross-section in the horizontal plane of the side shell 10 of the evaporation zone 5 of the downflow polymerization apparatus where the guide contacts the evaporation zone 5 may be any shape such as polygonal, elliptical, or circular.

Since the evaporation zone 5 is usually operated under reduced pressure, any evaporation zone 5 can be used as long as it can withstand this environment, preferably a circular or nearly circular shape. Therefore, the side shell 10 of the evaporation zone 5 is preferably cylindrical. In this case, it is preferable to provide a conical bottom housing at the lower part of the cylindrical side housing 10, and to provide a cylindrical liquid discharge port 7 at the lowermost part of the bottom housing.

In the guide contact flow polymerization device of the above-mentioned polycarbonate manufacturing device, the side and bottom shell of the evaporation zone 5 are respectively composed of the aforementioned cylindrical and conical parts, and the liquid discharge port 7 of the concentrated liquid or polymer is In the case of a cylindrical shape, when the inner diameter of the cylindrical portion of the side housing is D (cm), the length is L (cm), and the inner diameter of the liquid discharge port 7 is d (cm), D , L and d preferably satisfy the following formulas (X), (XI), (XII) and (XIII).

100≦D≦1800 Formula (X)

5≦D/d≦50 Formula (XI)

0.5≦L/D≦30 Formula (XII)

h-20≦L≦h+300 Formula (XIII)

h is the length of the guide 4 shown in the aforementioned <Condition (6)>.

In the aforementioned guide contact flow polymerization device, a more preferable range of D (cm) is 150≦D≦1500, and a more preferable range is 200≦D≦1200.

In addition, a more preferable range of D/d is 6≦D/d≦45, and a more preferable range is 7≦D/d≦40.

In addition, a more preferable range of L/D is 0.6≦L/D≦25, and a more preferable range is 0.7≦L/D≦20.

In addition, a more preferable range of L (cm) is h-10≦L≦h+250, and a more preferable range is h≦L≦h+200.

Regarding D, d, and L, the balance between the amount of the prepolymer that can be attached to the metal wire, the size of the polymerizer (D), and the size of the outlet d at the bottom of the polymerizer is preferably within the above range.

The number of metal wires = the size of the polymerizer (D) is determined relative to the supply amount of the prepolymer, and in order to take out the fallen polymer (the viscosity of the supplied prepolymer further increases as the polymerization proceeds) , sometimes it is necessary to use a piping diameter (d) corresponding to the viscosity.

On the other hand, since the liquid or melt is continuously supplied to the guide from the upper part, by satisfying the relationship of the above equation, a liquid having almost the same viscosity or a melt having an increased degree of polymerization having almost the same melt viscosity is obtained. The lower end of the guide member continuously drops to the bottom housing. That is, the liquid with almost the same viscosity or the polymer with almost the same degree of polymerization generated while flowing down the guide is collected in the lower part of the bottom shell, and a concentrated liquid with no change in evaporation degree or a liquid with no change in molecular weight is continuously produced. Polymer tendencies. This is one of the other excellent features of the guide contact flow polymerization apparatus constituting the above-mentioned polycarbonate manufacturing apparatus.

The concentrated liquid or polymer collected in the lower part of the bottom shell 11 is continuously taken out from the liquid discharge port 7 through the discharge pump 8. In the case of polymer, it is usually continuously granulated through an extruder or the like. In this case, additives, etc. can also be added through an extruder.

In addition, in the above-mentioned polycarbonate manufacturing apparatus, the liquid in the liquid supply area 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 area 3) to the upper surface of the porous plate 2 The available space volume V (m ³ ) and the upper area T (m ² ) of the porous plate 2 including the upper area of the holes preferably satisfy the following formula (XIV).

0.02(m)≦V/T≦0.5(m) Formula (XIV)

The aforementioned space volume V (m ³ ) is the actual liquid volume in the liquid supply area 3 during the continuous operation of the guide contact flow type polymerization apparatus, and is the volume excluding the flow path control member 20.

The liquid retention amount in the liquid supply area 3 is V (m ³ ). When this amount is small, the residence time in the liquid supply area 3 is shortened, and there will be no adverse effects caused by thermal denaturation. However, in order to make the process It is preferable to supply the liquid to the holes of the multi-well plate 2 as uniformly as possible so that the evaporated liquid becomes 1 ton/hr or more and the concentrated liquid and/or polymer with a predetermined degree of concentration or polymerization can be stably obtained for a long time. Therefore, the value of V/T is preferably within the range of the aforementioned formula (XIV). A better range of V/T value is 0.05(m)≦V/T≦0.4(m), and a better range is 0.1(m)≦V/T≦0.3(m).

Furthermore, in the guide contact flow polymerization device of the above-mentioned polycarbonate manufacturing device, the space volume V (m ³ ) where the liquid can exist in the aforementioned liquid supply zone 3 and the space volume Y (m ³ ) of the evaporation zone 5 are, Preferably, it satisfies the following formula.

10≦Y/V≦500

In order to evaporate a large amount of liquid per unit time stably and efficiently over a long period of time without causing a decrease in physical properties due to thermal denaturation, the Y/V value is preferably within this range. A better Y/V value range is 15≦Y/V≦400, and a better range is 20≦Y/V≦300.

The space volume Y (m ³ ) of the evaporation zone 5 is the space volume from the lower surface of the porous plate 2 to the liquid discharge port 7, and includes the volume occupied by the guide.

In the guide member constituting the above-mentioned polycarbonate manufacturing device, in the contact flow polymerization device, the liquid or gaseous substance or the molten prepolymer does not enter the cylindrical shape or inside of the guide member 4 with an outer diameter r (cm). When the form is tubular, the outer diameter r (cm) preferably satisfies the following formula (XV).

0.1≦r≦1 Formula (XV)

The guide 4 allows the liquid or molten prepolymer to flow downward while performing evaporation, concentration or polymerization reaction, and also has the function of maintaining the liquid or molten prepolymer for a certain period of time. This holding time is related to the evaporation time or polymerization reaction time. As the evaporation or polymerization proceeds, the liquid viscosity or melt viscosity will increase, so the holding time and holding amount tend to increase. The amount of liquid or molten prepolymer retained by the guide 4, even at the same melt viscosity, differs due to the external surface area of the guide 4, that is, in the case of a cylinder or a tube, its outer diameter.

In addition, in addition to the quality of the guide 4 itself, the guide 4 provided in the guide contact flow downflow polymerization device preferably has a strength sufficient to support the mass of the liquid or molten prepolymer or polymer being retained. In this sense, the thickness of the guide 4 is important, and in the case of a cylindrical or tubular shape, it is better to satisfy the aforementioned formula (XV).

When the outer diameter r (cm) of the guide 4 is 0.1 or more, stable operation for a long time tends to be possible in terms of strength. In addition, by setting r (cm) to be 1 or less, it is possible to prevent the guide itself from becoming extremely heavy, such as the tendency of having to be extremely thickened to keep them in contact with the guide during downflow polymerization. Defects such as the thickness of the porous plate 2 of the device can prevent an increase in the amount of retained liquid or molten prepolymer or polymer, and can prevent defects such as changes in concentration or increase in molecular weight.

In this sense, a better range of the outer diameter r (cm) of the guide 4 is 0.15≦r≦0.8, and a better range is 0.2≦r≦0.6.

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 are not particularly limited as long as the liquid or raw material molten prepolymer or polymer can come into contact with the guide and flow down.

The guide 4 and the porous plate 2 may be in contact with each other or not.

It is preferable that the guide 4 is arranged corresponding to the holes of the porous plate 2, but it is not limited to this. The reason for this is that the liquid or raw material molten prepolymer or polymer dropped from the porous plate 2 is designed to contact the guide 4 at an appropriate position.

A preferred way to arrange the guide 4 corresponding to the holes of the porous plate 2 is as follows: (1) Fix the upper end of the guide on the lower surface of the flow path control member, etc., and insert the guide through the porous plate. The method of setting the guide near the center of the hole; or (2) fixing the upper end of the guide to the peripheral edge of the upper end of the hole in the porous plate, and setting the guide in a state where the guide penetrates the hole in the porous plate. or (3) fixing the upper end of the guide to the lower side of the porous plate, etc.

The method of causing the liquid or raw material molten prepolymer or polymer to flow down along the guide 4 through the perforated plate 2 is not particularly limited. Examples include: a method of flowing down by the liquid height difference or its own weight, or using a pump, etc. Methods such as pressurizing and extruding liquid or raw material molten prepolymer or polymer from the porous plate 2 are used. A preferred method is to use a supply pump and supply a predetermined amount of liquid or raw material molten prepolymer or polymer to the liquid supply area of the evaporation device under pressure, so that the liquid or raw material is introduced into the guide 4 through the porous plate 2 A method in which molten prepolymer or polymer flows down a guide by its own weight.

In the above-mentioned polycarbonate manufacturing device, the preferred material of such a guide is selected from metals such as stainless steel, carbon steel, Hoechst alloy, nickel, titanium, chromium, aluminum and other alloys, or a polymer with high heat resistance Materials etc. A particularly good material is stainless steel.

In addition, the surface of the guide can be subjected to various treatments such as plating, lining, passivation, acid cleaning, solvent and phenol cleaning, etc. as needed.

By using the above-mentioned polycarbonate manufacturing equipment, it is possible to stably produce polycarbonate at a fast evaporation rate or a fast polymerization rate on an industrial scale for a long time (without causing changes in molecular weight during polymer production). The reason why a high-quality and high-performance concentrated liquid or polymer is colored and has good hue and excellent mechanical properties is not yet clear, but it can be speculated as follows.

That is, in the guide contact flow polymerization device constituting the above-mentioned polycarbonate manufacturing device, the liquid of the raw material is introduced into the guide 4 from the liquid receiving port 1 through the liquid supply area 3 and the porous plate 2, and flows along the guide 4 4. The lower side is concentrated or the degree of polymerization increases. In this case, since the liquid or molten prepolymer undergoes effective internal stirring and surface renewal while flowing down the guide, and effectively removes low-boiling point substances, concentration or polymerization is performed at a faster speed. Since the viscosity gradually increases as concentration or polymerization proceeds, the adhesion force relative to the guide 4 increases, and the amount of liquid or melt adhering to the guide 4 increases as it moves toward the lower part of the guide 4 . This means the residence time of liquid or molten prepolymer on the guide, that is, the increase in evaporation time or polymerization time. In addition, since the surface per unit weight of the liquid or molten prepolymer flowing down by its own weight while being supported by the guide 4 is extremely large and its surface is renewed efficiently, it becomes easy to evaporate as conventionally known. Evaporation and concentration in high viscosity areas which are extremely difficult to achieve in equipment or mechanically stirred polymerizers, or high molecular weight in the second half of polymerization. This is one of the excellent features of the above-mentioned polycarbonate manufacturing apparatus.

In the guide contact flow polymerization device constituting the above-mentioned polycarbonate manufacturing device, in the second half of evaporation or polymerization, although the amount of liquid or melt adhering to the guide 4 increases, it is only corresponding to its viscosity. Due to the adhesive holding force, at the same height of the plurality of guides 4, almost the same amount of liquid or melt with almost the same viscosity is supported on each guide 4. On the other hand, since the liquid or melt is continuously supplied to the guide 4 from the upper part, the liquid with almost the same viscosity or the melt with a further increased degree of polymerization having almost the same melt viscosity is continuously supplied from the lower end of the guide 4 The ground falls to the bottom shell. That is, the liquid with almost the same viscosity or the polymer with almost the same degree of polymerization generated by flowing down the guide is collected in the lower part of the bottom shell, and a concentrated liquid with no change in evaporation degree or a liquid with no change in molecular weight is continuously produced. of polymers tendency. This is one of the other excellent features of the above-mentioned guide contact flow polymerization device. The concentrated liquid or polymer collected in the lower part of the bottom shell is continuously taken out through the liquid discharge port 7 by the discharge pump 8. In the case of polymer, it is usually continuously granulated through an extruder or the like. . In this case, additives, etc. can also be added through an extruder.

The porous plate 2 constituting the guide contact flow polymerization device is not particularly limited, and is usually selected from, for example, a flat plate, a corrugated plate, a plate with a thick central portion, and the like. The shape of the cross section of the porous plate 2 is not particularly limited, and is usually selected from circular, elliptical, triangular, polygonal and other shapes.

The cross-section of the holes of the porous plate is not particularly limited, and is usually selected from shapes such as circles, ellipses, triangles, slits, polygons, stars, etc.

The cross-sectional area of the hole is usually in the range of, for example, 0.01 to 100 cm ² , preferably 0.05 to 10 cm ² , and more preferably 0.1 to 5 cm ² . The distance between holes is measured by the distance between the centers of the holes, which is usually, for example, 1 to 500 mm, preferably 10 to 100 mm. The holes of the porous plate 2 can be holes that penetrate the porous plate 2 , or the tubes can be installed on the porous plate 2 . In addition, it can also be tapered.

In the aforementioned guide contact flow polymerization apparatus, the porous plate 2 and its holes preferably satisfy the formulas (VI) and (VII) as described above.

In addition, the guide 4 constituting the guide contact flow polymerization device does not have a heating source such as a heat medium or an electric heater inside itself, and is preferably an average length relative to the outer circumference of the cross section in the horizontal direction. Made of material with a very large length ratio perpendicular to the cross section. The ratio (length in the direction perpendicular to the cross section/average length of the outer circumference of the cross section in the horizontal direction) is usually in the range of, for example, 10 to 1,000,000, preferably in the range of 50 to 100,000.

The shape of the cross section in the horizontal direction of the guide 4 is not particularly limited, and is usually selected from shapes such as circles, ellipses, triangles, quadrangles, polygons, stars, and the like. Section of guide 4 The shapes of the faces can be the same or different along the length. In addition, the guide 4 may be hollow. A major feature of the guide 4 constituting the above-mentioned polycarbonate manufacturing apparatus is that since it does not have a heating source, there is no concern that thermal denaturation of the liquid will occur on the surface of the guide 4 .

The guide 4 may be in the shape of a metal wire or a thin rod, or may be formed into a single shape such as a thin tube in such a manner that liquid or molten prepolymer does not enter the inside, or may be formed by twisting or other methods. And those who combine plural kinds. In addition, it may also be mesh-shaped or stamped plate-shaped.

The surface of the guide 4 may be smooth or have uneven surfaces, or may have protrusions in part. Preferable guides 4 are cylindrical such as metal wires or thin rods, the aforementioned thin tubes or meshes, or stamped plates.

Among the guide contact flow-type polymerization apparatus constituting the above-mentioned polycarbonate manufacturing apparatus that can produce high-quality concentrated liquids or polymers on an industrial scale (output, long-term stable production, etc.), the particularly preferred one is: A type of guide member in which a lateral support member is used from the upper part to the lower part of the metal wire-shaped, thin rod-shaped or thin tube-shaped guide member 4 and is connected at appropriate intervals above and below.

For example, from the upper part to the lower part of a plurality of metal wire-shaped or thin rod-shaped or thin tube-shaped guides, use transverse support materials and fix them at appropriate intervals above and below, for example, at intervals of 1 cm to 200 cm, to create a grid shape. Or mesh guides, and then arrange a plurality of grid-like or mesh-like guides at the front and rear, and then use horizontal support materials with appropriate intervals above and below, such as 1cm to 200cm intervals, to combine the three-dimensional structure they form. guides; or use horizontal support materials and fix the climb formed by a plurality of metal wire-shaped or thin rod-shaped or thin tube-shaped guides at appropriate intervals above and below, such as 1cm to 200cm. Rack-shaped three-dimensional guide.

The horizontal support members are not only beneficial to maintaining the spacing between the guides at almost the same level, but are also beneficial to strengthening the overall strength of the flat or curved guides or the three-dimensional guides. These support materials may be the same or different materials as the guide members.

The guide contact flow polymerization device constituting the polycarbonate manufacturing device is preferably a device that evaporates the low-boiling-point substance from a liquid containing a substance with a lower boiling point than the liquid.

Although this liquid can be at normal temperature, it is usually preferably supplied from the liquid receiving port to the guide contact flow-down polymerization device in a heated state. In addition, when the guide contacts the outer wall surface of the downflow polymerization device, it is usually better to be provided with a sheath. The sheath can also be heated by water vapor or heat medium as needed, thereby performing the liquid supply zone 3 or Heating and/or heat preservation of the flow path control member 20 or the porous plate 2, and heat preservation of the evaporation zone 5 or the porous plate 2, etc.

The above-mentioned guide contact flow polymerization device can be used not only as a simple liquid concentration device, but also as a polymerization device for condensation polymers or low boiling point substances containing monomers, oligomers, or by-products. A device for purifying thermoplastic polymers, a device for separating and recovering thermoplastic polymers from a solution, and an evaporation device for liquids with relatively high viscosity.

Therefore, the liquid supplied from the liquid supply zone is a monomer for producing the condensation polymer, a mixture of two or more monomers, a prepolymer of the condensation polymer, or a melt of the condensation polymer, and has a low boiling point. The by-product substances and/or oligomers generated in the polycondensation reaction, and the low boiling point substances are evaporated and removed from the aforementioned melt, thereby being used as prepolymers and/or for improving the condensation polymer. Or a polymerization device for a condensation polymer having a polymerization degree of the aforementioned polymer.

The condensation polymer is preferably aliphatic polycarbonate, polycarbonates such as polycarbonate and various copolycarbonates; polyester polycarbonates, etc.

By using a polycarbonate manufacturing device equipped with the above-mentioned guide contact flow polymerization device, it is possible to stably manufacture a condensation system with high purity and high performance without coloring, gel-like substances or solid impurities for a long time, with no change in molecular weight. polymer.

The above-mentioned guide contact flow polymerization device is suitable for evaporating and removing low-boiling point substances from liquids with relatively high viscosity.

For example, when the above-mentioned guide contact flow polymerization apparatus is used as a polymerizer for condensation-based polymers, in conventional polymerizers, a part of the liquid remains in a state of being heated for a long time. In such a place, the liquid retained in this way will cause denaturation such as coloration, gelation, cross-linking, ultra-high molecular weight, solidification, burning, and carbonization. Therefore, the disadvantages of gradual or concentrated mixing of these denatured substances into the polymer cannot be avoided. However, the above-mentioned The guide contact flow type polymerization device not only does not have this shortcoming, but also has excellent effects that previous polymerizers did not have.

That is, for example, when polymerizing a molten prepolymer obtained from a dihydroxy compound and a diaryl carbonate to produce polycarbonate, the reaction temperature usually needs to be in the range of 200 to 350°C, especially during polymerization. In the second half, the viscosity rises sharply and the aromatic monohydroxy compound produced by the equilibrium reaction must be removed from the ultra-high viscosity material. Even if the polymerizer so far is used, such as the transverse twin-axis stirring ultra-high viscosity The polymer reactor also requires a high temperature of 300°C or more and a high vacuum of 133 Pa or less to carry out the reaction for a long time. In addition, it is also difficult to produce high molecular weight products such as tablets.

However, in the guide contact flow-type polymerization apparatus constituting the above-mentioned polycarbonate manufacturing apparatus, effective surface renewal is performed with internal stirring, so polymerization can be performed at a relatively low temperature. combined reaction. Therefore, the preferred reaction temperature is 100 to 290°C, more preferably 150 to 270°C. It is a characteristic of the above-mentioned polycarbonate manufacturing apparatus that polymerization can be fully carried out at low temperatures compared to conventional mechanical stirring polymerizers. This also enables the production of high-quality polycarbonate without coloring or deterioration in physical properties. one of the reasons.

Furthermore, conventionally known polymerizers have disadvantages such as the penetration of air, etc. from the sealing part of the mixer under high vacuum or the mixing of impurities. However, in the above-mentioned guide contact flow polymerization device, since there is no mechanical It stirs continuously and has no sealing part of the mixer, so there is very little infiltration of air, etc. or mixing of impurities, and high-purity, high-performance polycarbonate can be produced.

When the above-mentioned polycarbonate manufacturing apparatus is used to produce a condensation polymer, as the polymerization reaction proceeds, low boiling point substances produced by the equilibrium reaction are removed from the reaction system to increase the reaction rate. Therefore, it is suitable to introduce inert gases such as nitrogen, argon, helium, carbon dioxide or lower hydrocarbon gases that will not have adverse effects on the reaction into the guide contact flow polymerization device, and the aforementioned low boiling point substances are accompanied by Methods to remove these gases; or methods to carry out reactions under reduced pressure, etc. Alternatively, a combination of these methods may be suitable. However, in this case, it is not necessary to bring a large amount of inert gas introduction guide into contact with the downflow polymerization device, and it is only necessary to maintain the interior in an inert gas environment.

In addition, when the above-mentioned polycarbonate production equipment is used to produce a condensation-based polymer, the reaction pressure in the guide contact flow polymerization equipment depends on the type of low-boiling point substances produced by by-products or the properties of the polymer to be produced. Depending on the type, molecular weight, polymerization temperature, etc., for example, when polycarbonate is produced from a molten prepolymer derived from bisphenol A and diphenyl carbonate, the number average molecular weight is preferably in the range of 5,000 or less. The range is 400 to 3,000PaA. When the number average molecular weight is 5,000 to 10,000, the range of 50 to 500PaA is preferred. around. When the number average molecular weight is 10,000 or more, it is preferably 300 PaA or less, and particularly preferably in the range of 20 to 250 PaA.

When the above-described guide contact flow polymerization apparatus is used as a polymerizer to produce a condensation-based polymer, a polymer having a desired degree of polymerization can be produced using only one guide contact flow polymerization apparatus. It is also possible to connect two or more guide contact flow-type polymerization devices to sequentially increase the polymerization degree in accordance with the degree of polymerization of the molten monomer or molten prepolymer used as raw materials or the yield of the polymer.

In this case, it is preferable that two or more guide contact flow polymerization devices are connected in series, in parallel, or in any combination of series and parallel.

In addition, in this case, in each guide contact flow polymerization apparatus, guides or reaction conditions suitable for the degree of polymerization of the prepolymer or polymer to be produced can be adopted.

For example, a first guide contact downflow polymerization device, a second guide contact downflow polymerization device, a third guide contact downflow polymerization device, and a fourth guide contact downflow polymerization device are used. ． ． ． When the degree of polymerization is increased sequentially, if the total external surface area of the entire guide member of each polymerization device is set to S1, S2, S3, and S4. ． ． ． , then it can be formed as S1≧S2≧S3≧S4≧. ． ． ． .

In addition, the polymerization temperature in each polymerization device may be the same temperature, or may be increased sequentially.

The polymerization pressure can also be reduced sequentially in each polymerization device.

In this sense, for example, when using two polymerization devices in which the first guide member contacts the downflow polymerization device and the second guide member contacts the downflow polymerization device and the degree of polymerization is increased in sequence, it is preferable to use: the first polymerization device The total external surface area S1 (m ² ) of the entire guide member of the device and the total external surface area S2 (m ² ) of the entire guide member of the second polymerization device satisfy the following formula (XVI):

1≦S1/S2≦20 formula (XVI)

By making S1/S2 equal to or greater than 1, it is possible to suppress fluctuations in molecular weight, perform stable production over a long period of time, and obtain desired yields.

By setting S1/S2 to 20 or less, the flow rate of the molten prepolymer flowing down along the guide in the second polymerization device can be suppressed. As a result, the residence time of the molten prepolymer can be sufficiently ensured to obtain the desired Molecular weight of the polymer. The better range is 1.5≦S1/S2≦15.

In the above-mentioned polycarbonate manufacturing apparatus, it is preferable to further provide an inert gas absorption device for supplying the inert gas to the pre-melt of the condensation polymer before the guide contacts the downflow polymerization device. absorbed by the polymer.

In addition, when a plurality of seat guides are connected and used in contact with a downflow polymerization device, it is preferable to separately provide an inert gas absorbing device for each polymerization device, and the inert gas absorbing device is used to supply the inert gas to the guide. It is absorbed by the molten prepolymer of the condensation polymer before the parts contact the downflow polymerization unit. Through the arrangement of the inert gas absorption device, the effect of the present invention can be further improved.

The following explains the case of using a guide contact flow polymerization device and an inert gas absorption device as a pair of devices.

The molten prepolymer is introduced into the inert gas absorption device before being supplied to the guide contact flow polymerization device. In the inert gas absorption device, by treating the molten prepolymer with an inert gas, the inert gas is absorbed by the molten prepolymer, and thereby absorbing 0.0001 to 1 N liters per 1 kg of the molten prepolymer in the molten prepolymer ( However, N liters is a specific amount of inert gas (the volume measured under standard temperature and pressure conditions), and then the molten prepolymer after absorbing this specific amount of inert gas is supplied to the guide contact flow polymerization device and Perform aggregation.

The so-called treating the molten prepolymer by inert gas means that the molten prepolymer absorbs the inert gas under conditions where the molten prepolymer is not easily polymerized.

The amount of inert gas absorbed by the molten prepolymer is preferably in the range of 0.0001 to 1 N liter per 1 kg of the molten prepolymer, more preferably in the range of 0.001 to 0.8 N liter, and still more preferably in the range of 0.005 to 0.6 N liter.

When the amount of absorbed inert gas is 0.0001 N liter or more per 1 kg of the molten prepolymer, the effect of increasing the polymerization speed achieved by using the inert gas to absorb the prepolymer and the use of the inert gas to absorb the prepolymer The achieved stable manufacturing effect of polycarbonate becomes greater. In addition, in this embodiment, the amount of absorbed inert gas does not need to be more than 1 N liter per 1 kg of the molten prepolymer. When the molten prepolymer that has absorbed this specific amount of inert gas is polymerized in a guide contact flow polymerization apparatus constituting the above-mentioned polycarbonate manufacturing apparatus, the effect of the present invention can be further enhanced.

The amount of inert gas that is caused to be absorbed by the molten polymer can usually be easily determined by directly measuring the amount of inert gas supplied. When the molten prepolymer is absorbed while circulating the inert gas in the inert gas absorption device, the amount of the absorbed inert gas can be determined from the difference between the amount of the supplied inert gas and the amount of the discharged inert gas. . In addition, it is also possible to supply a predetermined amount of molten prepolymer to an inert gas absorbing device into which an inert gas of a predetermined pressure is introduced, and reduce the pressure of the inert gas absorbing device due to the inert gas being absorbed into the molten prepolymer. Measured by quantity. Furthermore, this may be a batch method in which a predetermined amount of molten prepolymer is supplied to the absorption device in batches and the amount of inert gas absorbed is measured, or the molten prepolymer may be continuously supplied to the absorption device, and This is a continuous method that measures the amount of inert gas absorbed while taking it out continuously.

In this embodiment, it is preferable to use an inert gas absorption device and treat the molten prepolymer with inert gas under a predetermined pressure and under conditions where the molten prepolymer is not easily polymerized to absorb the inert gas.

Making the molten prepolymer absorb the inert gas means that the inert gas is dispersed and/or dissolved in the molten prepolymer.

Dispersion means a state in which the inert gas is mixed in the molten prepolymer in the form of bubbles to form a gas-liquid mixed phase. Dissolution means a state in which the inert gas and the molten prepolymer are mixed with each other to form a uniform liquid phase.

The inert gas is not only dispersed, but also dissolved in the molten prepolymer.

In order to effectively dissolve the inert gas in the molten prepolymer, it is better to increase the gas-liquid interface area to improve the contact efficiency, or to implement it under pressure of the inert gas.

As long as the inert gas absorbing device constituting the above-mentioned polycarbonate manufacturing device can allow the molten prepolymer to absorb the inert gas, the type is not particularly limited. Examples include: chemical device design. Operation Series No. 2, revised gas absorption pages 49 to 54 (issued by Chemical Industry Co., Ltd. on March 15, 1976) include packed tower type absorption equipment, scaffolding type absorption equipment, spray tower type absorption equipment, and flow filling Conventional devices such as tower-type absorption devices, liquid film cross-flow absorption devices, high-speed rotating flow absorption devices, mechanical force application absorption devices, or other conventional devices, or make one side of the molten prepolymer along the guide in an inert gas environment Devices for absorbing falling surfaces, etc.

In addition, it may also be a device in which an inert gas is directly supplied to a pipe that supplies the molten prepolymer to the guide contact flow polymerization device and is absorbed therein. The best method is to use a spray tower type absorption device or a device that absorbs while falling along the guide.

The inert gas absorption device is particularly preferably a device of the same type as the guide contact flow polymerization device.

Since the inert gas absorption device is operated under conditions where polymerization is almost not carried out, it is completely different from the polymerization device in terms of functionality. However, the outstanding feature of this type of device is that the melt per unit when flowing down the guide is The mass surface is extremely large, and the surface renewal and internal stirring of the melt are excellent. Accordingly, extremely effective inert gas absorption can be carried out in a short time.

Unlike the polymerization device, in the inert gas absorption device, since there is almost no change in the viscosity of the molten prepolymer at the upper and lower parts of the guide, the processing capacity of the molten prepolymer per unit time is large. Therefore, even if they are of the same type, the inert gas absorption device can generally be smaller than the guide contact flow polymerization device.

Next, preferred polycarbonate production in this embodiment will be described.

When the number average molecular weights of the molten prepolymer before and after inert gas absorption are M ₁ and M ₂ respectively, the molecular weight change (M ₂ -M ₁ ) before and after inert gas absorption is preferably substantially 2,000 or less, more preferably The price is less than 1,000, and preferably less than 500.

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

The pressure Pg (PaA) at which the molten prepolymer absorbs the inert gas is preferably higher than the pressure used to produce the molten prepolymer.

That is, it is preferably the same reaction pressure as that used when producing a molten prepolymer of polycarbonate by reacting a dihydroxy compound and a diaryl carbonate, or under a pressure condition higher than this reaction pressure. To absorb inert gases.

In addition, Pg (PaA) is a pressure higher than the pressure Pp (PaA) of the subsequent polymerization reaction in the guide contact flow polymerization device, and relative to M ₁ (as defined above), preferably satisfies the following formula relationship.

Formula: Pg>4×10 ¹² ×M ₁ ^-2.6871

When Pg (PaA) satisfies the relationship of the above formula, the effect of increasing the polymerization speed achieved by using the inert gas absorbing prepolymer and the stable manufacturing effect of polycarbonate achieved by using the inert gas absorbing prepolymer become big.

It is particularly preferable to set the pressure when absorbing the inert gas to normal pressure or pressurization in order to increase the absorption rate of the inert gas in the molten prepolymer and thereby reduce the size of the absorption device.

The upper limit of the pressure during inert gas absorption is not particularly limited, but the inert gas is usually absorbed at a pressure of 2×10 ⁷ PaA or less, preferably 1×10 ⁷ PaA or less, and more preferably 5×10 ⁶ PaA or less. .

The method of causing the molten prepolymer to absorb the inert gas in the inert gas absorbing device may be a method of causing most of the inert gas supplied to the inert gas absorbing device to be absorbed by the molten prepolymer, or the method may be a method of absorbing the supplied inert gas into the inert gas absorbing device. A method in which part of the gas is absorbed into the molten prepolymer.

The former method is not particularly limited, and examples include using a spray tower type absorption device or a device that absorbs while falling along a guide to supply an inert gas that is almost the same amount as the inert gas absorbed by the molten prepolymer. , and the method of absorbing while maintaining the pressure of the absorption device almost constant; or the method of directly supplying the inert gas to the absorption device in the pipe that supplies the molten prepolymer to the polymerizer, etc.

In addition, the latter method is not particularly limited, and examples thereof include using a spray tower type absorption device or a device that absorbs molten prepolymer while falling along a guide as an inert gas absorber. A method of circulating the inert gas above the level absorbed by the molten prepolymer in the absorption device, and then discharging the excess inert gas from the inert gas absorption device.

In terms of further reducing the amount of inert gas used, the former method is particularly preferred.

In addition, the absorption of inert gas is a continuous method in which the molten prepolymer is continuously supplied to the absorption device to absorb the inert gas, and then the molten prepolymer that has absorbed the inert gas is continuously taken out; and the molten prepolymer is processed in batches. Any batch method of absorbing inert gas by putting it into an absorption device can be used.

The so-called inert gas is a general term for gases that do not cause chemical reactions with molten prepolymers and are stable under polymerization conditions. The inert gas is not particularly limited, and examples thereof include nitrogen, argon, helium, carbon dioxide, organic compounds that are gaseous at a temperature at which the prepolymer remains in a molten state, and lower hydrocarbon gases with 1 to 8 carbon atoms. wait. A particularly preferred inert gas is nitrogen.

In the manufacturing method of polycarbonate according to this embodiment, in the guide contact flow polymerization apparatus, in order to provide the molten prepolymer in the supply pipe from the inert gas absorber to the guide contact flow polymerization apparatus, To maintain the pressure of the molten prepolymer that has absorbed the inert gas at a predetermined pressure, it is preferable to install a predetermined pressure adjustment valve in front of the inlet of the guide contacting the downflow polymerization device, and thereby control the pressure of the molten prepolymer.

The inside of the downflow polymerization device in contact with the guide member is in a relatively high vacuum. The molten prepolymer near the supply port of the device is attracted by the device and easily becomes a lower pressure state. Therefore, the inert gas absorbed in the inert gas absorbing device sometimes separates from the molten prepolymer and condenses. Therefore, in order to prevent such a situation, it is preferable to supply the inert gas while maintaining a pressure higher than the pressure at which the inert gas is absorbed by the molten prepolymer in the inert gas absorbing device.

Specifically, the range of 15 kPaA to 200 kPaA is preferable, the range of 20 kPaA to 150 kPaA is more preferable, and the range of 20 to 100 kPaA is more preferable.

When a pressure regulating valve is installed, or when the pressure is higher than the pressure that causes the inert gas to be absorbed by the molten prepolymer, the pressure of the molten prepolymer in the pipe becomes stable, which can suppress the gas that has been absorbed into the molten prepolymer. The separation and condensation of inert gases such as nitrogen in the polymer, and the uniformity of the molten prepolymer are stabilized, and the uniform and continuous foaming phenomenon of the molten prepolymer is maintained in the guide contact flow polymerization device, which can produce stable products, and has the tendency to inhibit the improvement of color tone and the generation of impurities such as fish eyes and gel.

On the other hand, even if it exceeds 200kPaA, the effect will not change. Instead, it will cause excessive load on the discharge gear pump or piping of the inert gas absorption device, and the pressure resistance must be improved. This is not feasible in practice, so the upper limit is better. The system is set to 200kPaA.

The polycarbonate manufacturing device used in this embodiment is preferably one that satisfies the above-mentioned conditions and has mechanical strength corresponding thereto. Devices or equipment having any other functions required for continuous operation may also be added.

In addition, the polycarbonate manufacturing apparatus used in this embodiment may be one in which a plurality of the above-mentioned guide contact flow polymerization apparatuses and inert gas absorption apparatuses are connected, and may be additionally provided with any other functions other than evaporation. device or equipment.

In the manufacturing method of this embodiment, when a molten prepolymer obtained from a dihydroxy compound and a diaryl carbonate compound is polymerized using a guide contact flow polymerization apparatus to manufacture polycarbonate, the polymerization zone The preferred reaction pressure varies depending on the type or molecular weight of the polycarbonate to be produced, the polymerization temperature, etc. The number average molecular weight is in the range of 17,000 or less, preferably in the range of 400 to 3,000 Pa, and the number average molecular weight is in the range of 17,000 to 17,000. 34,000 In this case, the range of 50 to 500Pa is preferred. When the number average molecular weight is 34,000 or more, it is preferably 300 Pa or less, and particularly preferably in the range of 20 to 250 Pa.

In the polycarbonate manufacturing method of this embodiment, various additives can be added. For example, the polycarbonate obtained in the second guide contact flow polymerization apparatus 48A and 48B can be obtained from the second guide in a molten state. The contact flow polymerization devices 48A and 48B are transferred to the subsequent machines 50A and 50B.

The latter machines 50A and 50B are not particularly limited as long as they are machines that have received molten polycarbonate in the past. Examples include extruders, granulators, screening machines, dryers, silos, and packaging machines.

For example, molten polycarbonate can be supplied to an extruder, and other resins such as ABS or PET, or heat-resistant stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, and mold release materials can be mixed in the extruder. Additives such as agents, flame retardants, organic or inorganic pigments or dyes, metal deactivators, antistatic agents, lubricants, nucleating agents and other optional additives.

These other resins and optional additives can be used individually by 1 type or in combination of 2 or more types.

[Polycarbonate]

The polycarbonate of this embodiment has a structural unit represented by the following formula (2).

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and a cycloalkyl group with 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. .

In the polycarbonate of this embodiment, among all the structural units, the structural unit represented by formula (2) preferably contains more than 40 mol%, more preferably more than 50 mol%, and still more preferably 60 mol%. above. In the polycarbonate of this embodiment, the upper limit of the ratio of the structural units represented by formula (2) is not particularly limited, but is, for example, 100 mol%.

In addition, the terminal group of the polycarbonate of this embodiment is generally preferably a hydroxyl group and/or an aryl carbonate group represented by the following formula (AA).

In the formula, Ar ⁵ has the same definition as the aforementioned Ar ³ and Ar ⁴ .

Furthermore, the polycarbonate of this embodiment may also contain a compound selected from the group consisting of an aliphatic diol compound represented by the following formula (3), an alicyclic diol compound, and a bisphenol compound. Constituent unit of more than one glycol.

HO-R ₅ -OH (3)

In the formula, R ₅ represents an alkylene group having 2 to 12 carbon atoms.

The "structural unit derived from diol" here means a structural unit in which the hydroxyl group of the diol is substituted with a carbonate group.

More specifically, the polycarbonate of this embodiment preferably has a structural unit represented by the following formula (Z).

In the aforementioned formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group having 5 to 10 carbon atoms in the ring structure. The group and ring constitute a carbocyclic aromatic group having 5 to 10 carbon atoms, and a carbocyclic aralkyl group having 6 to 10 carbon atoms. R ₅ represents hydrogen or an alkylene group having 1 to 6 carbon atoms. In addition, among R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , more than one hydrogen atom can be substituted by other substituents, such as halogen atoms, carbon number, etc. within the scope that will not adversely affect the reaction. Substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a vinyl group, a cyano group, an ester group, a amide group, a nitro group, etc.

In the polycarbonate of this embodiment, in all structural units, these structural units preferably contain 10 mol% or more and 60 mol% or less, more preferably 15 mol% or more and 50 mol% or less, and still more preferably It is more than 20 mol% and less than 40 mol%.

The melt volume flow rate (MVR) in the polycarbonate of this embodiment is preferably 40cm ³ /10min or less at 230°C, more preferably 30cm ³ /10min or less, and still more preferably 20cm ³ /10min or less. The best value is 10cm ³ /10min or less. The lower limit of the melt volume flow rate (MVR) in the polycarbonate of this embodiment is not particularly limited, but is, for example, 0.5 cm ³ /10 min.

The melt volume flow rate (MVR) in the polycarbonate of this embodiment is preferably 70cm ³ /10min or less at 270°C, more preferably 60cm ³ /10min or less, and still more preferably 55cm ³ /10min or less. The best is 50cm ³ /10min or less. The lower limit of the melt volume flow rate (MVR) in the polycarbonate of this embodiment is not particularly limited, but is, for example, 1.5 cm ³ /10 min.

In this embodiment, the melt volume flow rate (MVR) can be measured by the method described in the examples.

The haze in the polycarbonate of this embodiment is preferably 0.8% or less.

In this embodiment, the haze can be measured by the method described in the Examples.

The b* value in the polycarbonate of this embodiment is preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.30 or less.

In this embodiment, the b* value can be measured by the method described in the examples.

The polycarbonate of this embodiment can be produced by the above-described polycarbonate production method.

As is clear from the above description, polycarbonate can be continuously produced by the production method of this embodiment.

The polycarbonate obtained by the polycarbonate manufacturing method of this embodiment can be formed into a molded article through a predetermined molding step.

The molding step is not particularly limited as long as it is a conventional molding step. For example, an injection molding machine, an extrusion molding machine, a blow molding machine, a sheet molding machine, etc. can be used to mold polycarbonate to obtain a molded article.

The obtained molded products can be used in a wide range of applications such as automobiles, electrical, electronics, OA, optical media, building materials, and medical care.

Example

The present invention is specifically described below using specific examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

The measurement methods of each physical property and each characteristic in the following Examples and Comparative Examples are shown below.

[Physical properties and characteristics]

((1) Molecular weight, number average molecular weight (Mn))

Use a gel permeation chromatograph (LC-20AD, manufactured by Shimadzu Corporation, TSK-gel G5000H HR×1 tube, TSK-gel G3000H HR×1 tube, TSK-gel G1000H HR×1 tube, RI detector), and Use chloroform as the eluent and measure the prepolymer or particles at a temperature of 40°C.

The molecular weight of the prepolymer or particles is determined from the calibration curve of standard monodisperse polystyrene (molecular weight: 100, 580, 1390, 2780, 4830, 9970, 19540, 51150, 113300, 224900, 483400).

((2) Measurement of haze and hue)

Using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 70°C, the fully dried polycarbonate pellets were continuously formed into a test piece of 50 mm in length x 90 mm in width x 3.0 mm in thickness to obtain a test piece.

Using a spectrophotometer (manufactured by Vista Hunter Lab), the obtained test piece was measured by the penetration method under a D65 light source and a viewing angle of 10°, and the haze and yellowness were expressed as b* values.

The haze system is qualified if it is less than 0.8%.

(CIE No.15 (ASTM E308) specification).

((3)Measurement of MVR)

Use a melt flow test device (Mflow, manufactured by Zwick Roell) to measure the melt volume of the fully dried polycarbonate pellets at 270°C and 1.2kg load or 230°C and 1.2kg load. flow rate (MVR).

(Unit: cm ³ /10min) (ISO1133 specification).

[Example 1]

Polycarbonate was produced in the following manner using a polycarbonate production apparatus having the structure shown in FIG. 5 .

In the polycarbonate manufacturing apparatus, the polymerization raw materials and the catalyst are put into the mixing tank 31 and mixed.

The solution is then transferred to the dissolved mixture storage tanks 33A and 33B by the transfer pump 32, and further transferred from there by the transfer pumps 34A and 34B, and is prepolymerized in the first polymerizer 35.

Furthermore, prepolymerization is performed in the second polymerizer 37 via the discharge gear pump 36 to obtain a polycarbonate prepolymer.

The polycarbonate prepolymer is transported to the first inert gas absorption device 39 through the supply pump 38, and if necessary, the pressure adjustment valve 41 is used to adjust the prepolymer that has absorbed the inert gas to the following guide for contact flow polymerization. The supply pressure of the device is then transported and supplied to the first guide contact flow polymerization device 42 to perform polymerization. Here, the phenol is discharged from the vent as a low molecular weight component.

The pressure regulating valve 41 may be constituted by, for example, a valve, but the structure is not limited as long as it can adjust the solubility of the inert gas. The same applies to the pressure regulating valves 47A and 47B described below.

Next, the polycarbonate prepolymer is transported to the second inert gas absorbing device 44 via the supply pump 43, and then transported from there via the supply pumps 46A and 46B. If necessary, the pressure adjustment valves 47A and 47B are used to adjust the supply pressure of the prepolymer that has absorbed the inert gas to the following guide contact flow polymerization device, and then transports it to the connected second guide contact flow polymerization device 48A. , 48B for aggregation. Here, phenol is discharged from the vent.

Then, it is transported by supply pumps 49A and 49B, and additives are added to the subsequent machines 50A and 50B to obtain the desired polycarbonate.

A schematic structural diagram of the first and second inert gas absorbing devices 39 and 44 is shown in FIG. 1 .

Since the device configuration of the inert gas absorbing devices 39 and 44 is substantially the same as that of the guide contact flow polymerization devices 42, 48A, and 48B described later, the same reference numerals are used for the common parts.

Regarding the first inert gas absorption device, in the inert gas absorption area, the upper part of the casing is cylindrical, and the tapered lower part constituting the casing is an inverted cone with an inner diameter of 0.5 m and two guides 4. The guide 4 has five metal wires with a diameter of 3 mm arranged at an interval of 8 cm to form a width of 32.3 cm and h = 4 m. Each of the five metal wires is vertically arranged at an interval of 25 cm. The metal wire has a diameter of 3 mm and a length of 32.3 cm. The upper end of the metal wire is directly installed on the porous plate 2. The distance between the two guides is 80 mm. The molten prepolymer is distributed on the porous plate 2 to each guide through 10 holes with a diameter = about 0.2 cm. A sheath (not shown in the figure) is installed on the outside of the first inert gas absorption device, and is heated by a heat medium. In addition, the second inert gas absorbing device has almost the same shape as the first inert gas absorbing device except that the diameter of the holes of the porous plate 2 is about 0.6 cm.

Regarding the first polymerization device of the guide contact flow type, it has the same structure as the inert gas absorption device. In the polymerization reaction zone, the upper part of the shell is cylindrical, and the conical lower part of the shell is an inverted cone, and its inner diameter It is 0.5m and has 2 guides. The guides are arranged with 5 metal wires with a diameter of 3mm at 8cm intervals to form a width of 32.3cm and h=4m. The upper ends of these guides are directly installed on the porous plate 2 .The distance between the two guides is 80mm.

The molten prepolymer is distributed on a porous plate (distribution plate) 2 to each guide 4 through 10 holes with a diameter = about 0.2 cm. A sheath (not shown in the figure) is installed on the outside of the first polymerization device of the guide contact flow type, and is heated by a heat medium. In addition, the second polymerization device of the guide contact flow type has almost the same shape as the first polymerization device of the guide contact flow type except that the diameter of the holes of the porous plate 2 is about 0.4 cm.

As shown in Figure 5, two inert gas absorbing devices (the first inert gas absorbing device 39 and the second inert gas absorbing device 44) and two guide contact flow polymerization devices (the first guide contact flow polymerization device) are used. Device 42, second guide flow-down polymerization device 48A), according to the first inert gas absorption device 39, first guide flow-down polymerization device 42, second inert gas absorption device 44, second guide flow-down polymerization device The polymerization apparatuses are arranged in series in sequence to form a polycarbonate manufacturing apparatus connected to the polymerization equipment, and polycarbonate is manufactured using this manufacturing apparatus.

The method for producing the polycarbonate of Example 1 is specifically described below.

200 kg of diphenyl carbonate (hereinafter referred to as "DPC-1") melted at 160°C was put into the mixing tank 31 (inner capacity: 1 m ³ ). Next, 120 ppb by mass of potassium hydroxide was added as a catalyst to diphenyl carbonate, and the added liquid was slowly added while heating and stirring so that the temperature of the mixed liquid in the mixing tank 31 was maintained above 100°C. DPC-1 is a dihydroxy compound (isosorbide) represented by the following formula (4) at the same mole.

When the temperature of the aforementioned mixed liquid reaches 180°C, it is transferred to a dissolved mixture storage tank (inner capacity: 1 m ³ ) 33A.

The reaction mixture maintained in the dissolution mixture storage tank 33A for 4 to 6 hours is passed through the reactors with different pore diameters provided in series between the dissolution mixture storage tank 33A and the stirring tank type first polymerizer 35 at a flow rate of 43 kg/hr. 2 polymer filters (not shown in the figure; pore size on the upstream side is 5 μm and pore size on the downstream side is 2.5 μm) for filtration.

The filtered reaction mixture is heated by a preheater (not shown in the figure) and supplied to the stirring tank type first polymerizer 35 . The liquid temperature at the outlet of the preheater is 210°C.

When the liquid level of the reaction mixture in the dissolution mixture storage tank 33A drops below a predetermined value, the supply source of the reaction mixture to the stirring tank type first polymerizer 35 is switched from the dissolution mixture storage tank 33A to the dissolution mixture storage tank 33B. The reaction mixture is fed to the first stirring tank type polymerizer 35 The supply is performed continuously by alternately switching the supply sources of the dissolved mixture storage tanks 33A and 33B every 3.9 hours and repeating this operation.

The dissolution mixture storage tanks 33A and 33B are both equipped with internal coils and sheaths, and are maintained at 180°C.

In the stirred tank type first polymerizer 35 and the stirred tank type second polymerizer 37, stirring is performed under reduced pressure, and the reaction mixture is polymerized while removing the generated phenol, thereby obtaining a molten prepolymer.

At this time, the temperature of the stirring tank type first polymerizer 35 is 210°C and the pressure is 13.3 kPaA, and the temperature of the stirring tank type second polymerizer 37 is 245°C and the pressure is 2.66 kPaA.

The obtained molten prepolymer of polycarbonate (number average molecular weight Mn: 3,600) was continuously supplied to the supply zone 3 from the liquid receiving port 1 of the first inert gas absorption device by the supply pump 38 .

The prepolymer passed through the porous plate 2 of the distribution plate of the first inert gas absorption device 39 and continuously supplied to the inert gas absorption zone 15 of the internal space absorbs the inert gas while flowing down the guide 4 .

The inert gas absorption zone 15 belonging to the internal space of the first inert gas absorption device 39 is supplied with nitrogen gas from the inert gas supply port 9 and is maintained at 180 kPaA.

The molten prepolymer (each 1 kg of the molten prepolymer contains 0.04 N liters of nitrogen) dropped from the bottom of the guide 4 to the tapered lower part 11 of the casing of the first inert gas absorbing device 39 is used as described above. The amount in the bottom of the device becomes almost constant, and is continuously discharged by the discharge pump 8 (corresponding to the symbol 40 in FIG. 5), and contacts the liquid receiving port 1 of the downflow polymerization device 42 through the first guide. The pressure regulating valve (41) keeps the pressure of the molten prepolymer entering the valve at 25 kPaA, and is continuously supplied to the liquid supply area 3 through the first guide contacting the liquid receiving port 1 of the downflow polymerization device 42 .

The aforementioned prepolymer continuously supplied to the evaporation zone 5 belonging to the internal space through the porous plate 2 belonging to the distribution plate of the first guide contact flow-down polymerization device 42 flows down the guide 4 while being melted and polymerized. The condensation method continuously performs the polymerization reaction of polycarbonate.

The evaporation zone 5 belonging to the internal space of the first guide contact flow polymerization device 42 is maintained at a pressure of 800 PaA through the vacuum vent 6.

The molten prepolymer of polycarbonate with an increased degree of polymerization (number average molecular weight Mn is 7,700) dropped from the lower part of the guide 4 to the tapered lower part 11 of the housing where the die guide contacts the downflow polymerization device 42 is The liquid is continuously taken out from the liquid discharge port 7 at a constant flow rate by the discharge pump 8 (corresponding to the symbol 43 in FIG. 5 ) so that the amount in the bottom becomes almost constant, and then continuously supplied to the second inert gas. Liquid supply zone 3 of the absorption device 44 .

The aforementioned molten prepolymer is continuously supplied to the inert gas absorption zone 15 belonging to the internal space through the porous plate 2 belonging to the distribution plate of the second inert gas absorption device 44 .

The molten prepolymer absorbs the inert gas while flowing down the guide 4 .

The inert gas absorption zone 15 belonging to the internal space of the second inert gas absorption device 44 is supplied with nitrogen gas from the inert gas supply port 9 and is maintained at 200 kPaA.

The molten prepolymer (each 1 kg of the molten prepolymer contains 0.05 N liter of nitrogen) dropped from the bottom of the guide 4 to the bottom shell 11 belonging to the tapered lower part of the shell of the second inert gas absorption device, It is continuously discharged in a certain amount by the discharge pump 8 (corresponding to the symbol 46A in Figure 5), and through the pressure regulating valve located at the liquid receiving port 1 of the second guide contact flow down polymerization device 48A. (47A), the pressure of the molten prepolymer entering the valve is maintained at 25 kPa and is continuously supplied to each supply zone 3.

The molten prepolymer is continuously supplied to the evaporation zone 5 belonging to the internal space through the porous plate 2 belonging to the second guide contacting the distribution plate in the downflow polymerization device, and is condensed by the melt while flowing down the guide 4 It is legal to carry out the polymerization reaction of polycarbonate continuously.

The evaporation zones belonging to the internal space of the second guide contact downflow polymerization device are each maintained at a pressure of 120 PaA through the vacuum vent 6.

The generated polycarbonate dropped from the lower part of the guide 4 to the bottom housing 11 belonging to the tapered lower part of the housing of the second guide contact flow-down polymerization apparatus is such that the amount in the bottom becomes almost constant. The polycarbonate is continuously taken out from the subsequent machine (50A) in the form of a bundle through the discharge pump 8 (49A), cooled, and then cut to obtain granular polycarbonate.

The output is 20kg/hr.

The additive system is set to no addition.

After 150 hours from the start of production, the granular polycarbonate for haze, hue, and MVR measurements was collected. The measurement results of each characteristic are shown in Table 1.

[Examples 2 to 9]

Except that the raw materials and conditions were changed as described in Table 1, the same procedure as in Example 1 was performed to obtain granular polycarbonate.

[Comparative example 1]

A stirred tank type polymerization apparatus was used as the polymerization apparatus instead of the guide contact flow type polymerization apparatus, and polycarbonate was produced as described below.

200 kg of diphenyl carbonate (DPC-1) melted at 160°C was put into the mixing tank 31 (inner capacity: 1 m ³ ). Next, 120 ppb by mass of potassium hydroxide was added as a catalyst to diphenyl carbonate, and the mixture was heated and stirred as described in Table 1 while maintaining the temperature of the mixed solution in the mixing tank above 100°C. The same mole of dihydroxy compound as that of DPC-1 was added (same as in Example 4).

When the temperature of the aforementioned mixed liquid reaches 180°C, it is transferred to a dissolved mixture storage tank (inner capacity: 1 m ³ ) 33A.

The reaction mixture kept in the dissolved mixture storage tank 33A for 4 to 6 hours was polymerized in the stirred tank first polymerizer 35 under the same conditions as in Example 4, and the entire amount of the obtained prepolymer was transferred to For other stirring tank type polymerization devices equipped with twin-shaft stirring blades, after the temperature is raised to 215°C, the polymerization reaction is performed at 2.66kPa for 30 minutes, and then the temperature is raised to 250°C within 30 minutes, and polymerization is carried out at 120Pa for 1 hour. Reaction to produce polycarbonate. The obtained polycarbonate was taken out from the outlet, cut after cooling, and granular polycarbonate for haze, hue, and MVR measurements was collected. The measurement results of each characteristic are shown in Table 1. The collected polycarbonate weighs approximately 210kg.

[Comparative Examples 2 and 3]

Polycarbonate was produced in the same manner as in Comparative Example 1 except that the raw material dihydroxy compound was changed as described in Table 1 below, and pelletized polycarbonate was collected. The measurement results of each characteristic are shown in Table 1. The collected polycarbonate was approximately 215 kg in Comparative Example 2 and 220 kg in Comparative Example 3.

[Comparative example 4]

As described in Table 1 below, the dihydroxy compound of the raw material was changed to the dihydroxy compound (isosorbide) represented by the following formula (4),

The polymerization temperature of the first stirring tank type polymerizer 35 was changed to 210°C, and then the conditions of the other stirring tank type polymerization device equipped with twin-shaft stirring blades were set to: after the temperature was raised to 245°C, it was carried out at 2.66 kPa for 30 minutes of polymerization reaction, and then the temperature was raised to 265°C within 30 minutes. Except for this, the production of polycarbonate was carried out in the same manner as in Comparative Example 1. However, after the temperature was raised to 265°C and the conditions were changed to 120 Pa and after about After 30 minutes, the load of the mixer increased. If this was done, the mixing capacity would be exceeded, so the temperature was raised to 270°C. However, the load continued to rise, so the temperature was raised further and polymerization was attempted to 305°C. However, since it exceeded the capacity of the mixer, the temperature was increased to 305°C. No further aggregation is possible.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Example 10]

Polycarbonate was produced in the following manner using a polycarbonate production apparatus having the structure shown in FIG. 5 .

In the first inert gas absorbing device 39, in the inert gas absorbing area 15 belonging to the internal space, the upper part of the side housing 10 is cylindrical, and the bottom housing 11, which is the lower part of the tapered shape constituting the side housing 10, is an inverted cone. , in Figure 1, it is assumed that L=500cm, h=400cm, D=200cm, d=20cm, C=150°.

In addition, the diameter of the guide 4 provided in the inert gas absorption zone 50 belonging to the internal space is 0.3cm, and the total external surface area S of the aforementioned guide 4 is 60m ² , located above the inert gas absorption zone 50 belonging to the internal space. The diameter of the holes in the multi-well plate is approximately 0.2cm.

In addition, the second inert gas absorbing device 44 has almost the same shape as the first inert gas absorbing device 39 except that the diameter of the holes of the porous plate is about 0.6 cm.

A schematic diagram of a guide-contact downflow polymerization apparatus is presented in FIG. 2 . This guide contact flow polymerization apparatus has a disk-shaped flow path control member 20 with a thickness of approximately 2 cm and a cylindrical guide 4 as shown in FIG. 3 .

In addition, FIG. 3 shows a schematic structural diagram of the upper part of the guide 4 in which the guide contacts the downflow type polymerization apparatus.

In the guide contact flow type polymerization apparatus, the flow path control member 20 is suspended from the upper portion and fixed at a distance of approximately 8 cm from the upper inner wall 23 of the liquid supply area 3 .

In addition, the distance between the inner side wall surface 22 of the liquid supply area 3 and the flow path control member 20 is about 9 cm, and the distance between the porous plate 2 and the flow path control member 20 is about 8 cm.

The peripheral edge of the disc-shaped flow path control member 20 is finely processed so that the vertical cross section becomes a semicircle with a radius of approximately 1 cm, so as to prevent liquid from remaining on the peripheral edge.

The material of this guide contact flow-down polymerization device is all stainless steel.

The discharge pump 8 is configured as a gear pump when the concentrated liquid has a high viscosity, and as a general liquid delivery pump when the viscosity is not too high.

The guide contact flow polymerizer 42 has a cylindrical side shell 10 and a conical bottom shell 11. In Figure 2, L=950cm and h=850cm.

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

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

In addition, the diameter of the aforementioned guide =0.3cm.

The average number of holes per 1 m ² of the porous plate 2 (pieces/m ² ) = approximately 500. The diameter of the holes in the porous plate = about 0.2cm. The ratio (T/Q) of the upper area T (m ² ) of the porous plate including the upper area of the holes to the total effective cross-sectional area Q (m ² ) of the holes (T/Q) is 1300.

In FIG. 2 , in the liquid supply area 3 , the liquid containing a low-boiling point substance supplied from the liquid receiving port 1 passes through the upper surface of the flow path control member 20 and the upper inner wall surface 23 of the supply area 3 . Between the space and between the inner side wall surface 22 of the supply area 3 and the flow path control member 20, the flow mainly flows from the peripheral part to the central part of the porous plate 2, and is uniformly distributed from the holes (21, etc.) of the porous plate 2 to 4 for each guide.

The guide contact flow polymerization device is provided with an inert gas supply port 9 at the lower part, and a vacuum vent 6 (usually connected to a gas condenser and a pressure reducing device) for taking out evaporates of low boiling point substances at the upper part.

A sheath or a heating tube for a heat medium is provided on the outside of the guide contact flow-down polymerization device, so that the heat medium can be maintained at a predetermined temperature.

The second guide contact flow polymerization apparatus 48A, 48B has a disk-shaped flow path control member 20 with a thickness of approximately 2 cm and a guide 4 in the structure shown in FIG. 3 .

The disc-shaped flow path control member 20 is suspended from the upper portion and fixed at a distance of about 8 cm from the upper inner wall surface 23 of the liquid supply area.

In addition, the distance between the inner side wall surface 22 of the liquid supply area and the flow path control member 20 is about 9 cm, and the distance between the porous plate 2 and the flow path control member 20 is about 8 cm.

The peripheral edge of the disc-shaped flow path control member 20 is finely processed so that the vertical cross section becomes a semicircle with a radius of approximately 1 cm, so as to prevent liquid from remaining on the peripheral edge.

In addition, the cross section of the connection portion between the inner side wall surface 22 of the liquid supply area and the porous plate 2 is finely processed into a concave shape on the inside as shown in FIG. 4, and the angle E of the rising portion is approximately 170 degrees.

The material of the guide contact flow polymerization device is all stainless steel.

A discharge pump 8 is provided at the lower part of the second guide contact flow polymerization device. When the concentrated liquid has high viscosity, it is configured as a gear pump. When the viscosity is not too high, it is configured as a general liquid delivery pump. Pump.

The second guide contact flow type polymerization device has a cylindrical side housing 10 and a tapered bottom housing 11.

The second guide contact flow polymerization device is shown in Figure 2, with L=1,000cm and h=900cm.

The inner diameter of the side shell of the evaporation zone 5 is D=500cm, the inner diameter of the liquid discharge port 7 of the conical bottom shell 11 is d=40cm, and C=155 degrees.

The total external surface area of the guide 4 as a whole is S=250m ² .

In addition, the outer diameter of the aforementioned guide =0.3cm.

The average number of holes per 1 m ² of the porous plate 2 (pieces/m ² ) = approximately 140. The diameter of the holes in the porous plate = about 0.4cm. The ratio (T/Q) of the upper area T (m ² ) of the porous plate including the upper area of the holes to the total effective cross-sectional area Q (m ² ) of the holes (T/Q) is 470.

The structure of the second guide contact downflow polymerization device in the supply zone 3 is the same as that of the first guide contact downflow polymerization device.

The above-mentioned inert gas absorption device and the first and second guide contact flow polymerization devices are all made of stainless steel except for the discharge pump 8 .

As shown in Figure 5, two inert gas absorbing devices (the first inert gas absorbing device 39 and the second inert gas absorbing device 44) and two guide contact flow polymerization devices (the first guide contact flow polymerization device) are used. device 42, the second guide contact flow-down polymerization device 48A, 48B), according to the first inert gas absorption device 39, the first guide contact flow-down polymerization device 42, the second inert gas absorption device 44, the second guide contact The downflow polymerization apparatus (two units arranged in parallel) are arranged in series in order to form a polycarbonate manufacturing apparatus connected to the polymerization equipment, and polycarbonate is manufactured using this manufacturing apparatus.

The manufacturing method of the polycarbonate of Example 10 is demonstrated concretely below.

40 tons of diphenyl carbonate (DPC-1) melted at 160°C was put into the mixing tank 31 (internal capacity: 120 m ³ ).

Next, 120 ppb by mass of potassium hydroxide was added as a catalyst to diphenyl carbonate, and the mixture was heated and stirred to maintain the temperature of the mixed solution in the mixing tank above 100°C, while adding the same amount within 1.8 hours. DPC-1 is the same molar dihydroxy compound (70 mol% of the compound represented by the following formula (4) (isosorbide) and 30 mol% of 1,3-propanediol).

When the dihydroxy compound is a solid, a weighing hopper equipped with a load cell meter is used for weighing. When it is a liquid, a Coriolis mass flow meter is used for weighing.

When the temperature of the mixture reaches 180°C, it is transferred to the dissolved mixture storage tank (inner capacity: 120 m ³ ) 33A within 1 hour.

The reaction mixture maintained in the dissolved mixture storage tank 33A for 4 to 6 hours is used at a flow rate of 14 tons/hr by arranging the pore diameters between the dissolved mixture storage tank 33A and the stirring tank type first polymerizer 35 in series. Two polymer filters (not shown in the figure; the pore size on the upstream side is 5 μm and the pore size on the downstream side is 2.5 μm) are used for filtration.

The filtered reaction mixture is heated by a preheater (not shown in the figure) and supplied to the stirring tank type first polymerizer 35 . The liquid temperature at the outlet of the preheater is 230°C.

When the liquid level of the reaction mixture in the dissolution mixture storage tank 33A drops below a predetermined value, the supply source of the reaction mixture to the stirring tank type first polymerizer 35 is switched from the dissolution mixture storage tank 33A to the dissolution mixture storage tank 33B. The reaction mixture is supplied to the stirring tank type first polymerizer 35 continuously by alternately switching the supply source of the dissolved mixture storage tanks 33A and 33B every 3.9 hours and repeating this operation.

The dissolution mixture storage tanks 33A and 33B are both equipped with internal coils and sheaths, and are maintained at 180°C.

In the stirred tank type first polymerizer 35 and the stirred tank type second polymerizer 37, the reaction mixture is polymerized while stirring under reduced pressure and removing the generated phenol, thereby obtaining a prepolymer.

At this time, the temperature of the stirring tank type first polymerizer 35 is 200°C and the pressure is 13.3 kPaA, and the temperature of the stirring tank type second polymerizer 37 is 215°C and the pressure is 2.66 kPaA.

The obtained molten prepolymer of polycarbonate (number average molecular weight Mn: 3,600) was continuously supplied to the supply zone 3 from the liquid receiving port 1 of the first inert gas absorption device by the supply pump 38 .

The prepolymer continuously supplied to the inert gas absorption zone 15 belonging to the internal space through the porous plate 2 of the distribution plate of the first inert gas absorption device 39 absorbs the inert gas while flowing down the guide 4.

The inert gas absorption zone 15 belonging to the internal space of the first inert gas absorption device 39 is supplied with nitrogen gas from the inert gas supply port 9 and is maintained at 180 kPaA.

The molten prepolymer (each 1 kg of the molten prepolymer contains 0.04 N liters of nitrogen) dropped from the bottom of the guide 4 to the tapered lower part 11 of the casing of the first inert gas absorbing device 39 is used as described above. The amount in the bottom of the device becomes almost constant, and is continuously discharged by the discharge pump 8 (corresponding to the symbol 40 in FIG. 5), and the pressure of the liquid receiving port 1 of the first guide contact flow-down polymerization device 42 The pressure of the molten prepolymer entering the valve (41) is maintained at 25 kPaA, and the molten prepolymer is continuously supplied to the liquid supply area 3 through the first guide contacting the liquid receiving port 1 of the downflow polymerization device 42.

The prepolymer continuously supplied to the evaporation zone 5 belonging to the internal space through the porous plate 2 belonging to the distribution plate of the first guide contact flow-down polymerization device 42 flows down the guide 4 while being melted. The polycondensation method continuously performs the polymerization reaction of polycarbonate.

The evaporation zone 5 belonging to the internal space of the first guide contact flow polymerization device 42 is maintained at a pressure of 800 PaA through the vacuum vent 6.

The molten prepolymer of polycarbonate with an increased degree of polymerization (number average molecular weight Mn is 7,800) dropped from the lower part of the guide 4 to the tapered lower part 11 of the housing where the die guide contacts the downflow polymerization device 42 is The liquid is continuously taken out from the liquid discharge port 7 at a constant flow rate by the discharge pump 8 (corresponding to the symbol 43 in FIG. 5) so that the amount in the bottom becomes almost constant, and then continuously supplied to the second inert gas absorber. Liquid supply area 3 of device 44.

The aforementioned molten prepolymer is continuously supplied to the inert gas absorption zone 15 belonging to the internal space through the porous plate 2 belonging to the distribution plate of the second inert gas absorption device 44 .

The molten prepolymer absorbs the inert gas while flowing down the guide 4 .

The inert gas absorption zone 15 belonging to the internal space of the second inert gas absorption device 44 is supplied with nitrogen gas from the inert gas supply port 9 and is maintained at 200 kPaA.

The molten prepolymer (each 1 kg of the molten prepolymer contains 0.05 N liter of nitrogen) dropped from the bottom of the guide 4 to the bottom shell 11 belonging to the tapered lower part of the shell of the second inert gas absorption device, The three-way polymer valve (45) divides the polymer into two parts (divided at a ratio of 50:50), and the amount in the bottom becomes almost constant, and the discharge pump 8 (equivalent to the equivalent in Figure 5 Symbols 46A, 46B) are continuously discharged in a certain amount, and through the pressure regulating valve (47A, 47B) located at the liquid receiving port 1 of the second guide contact flow down polymerization device 48A, 48B, the melt prepolymer entering the valve is The pressure of the material is maintained at 220kPa and is continuously supplied to each supply zone 3.

The molten prepolymer is continuously supplied to the evaporation zone 5 belonging to the internal space through the perforated plate 2 belonging to the second guide contacting the distribution plate in the downflow polymerization device, and flows down along the guide 4 by the molten prepolymer. The condensation method continuously performs the polymerization reaction of polycarbonate.

The evaporation zones belonging to the internal space of the second guide contact downflow polymerization device are each maintained at a pressure of 120 PaA through the vacuum vent 6.

The generated polycarbonate dropped from the lower part of the guide 4 to the bottom housing 11 belonging to the tapered lower part of the housing of the second guide contact flow-down polymerization apparatus is such that the amount in the bottom becomes almost constant. Granular polycarbonate is obtained by continuously taking out the polycarbonate in the form of a bundle from the subsequent machine (50A, 50B) through the discharge pump 8 (49A, 49B), and cutting it after cooling.

The output is 4.3 tons/hr respectively (total 8.6 tons/hr).

The additive system is set to no addition.

After 150 hours from the start of production, the particles for haze, hue, and MVR measurements were collected.

Each measurement or test is performed using the polycarbonate obtained from the subsequent machine 50A.

Regarding the subsequent machine 50B, since the manufacturing conditions are the same as those of the polycarbonate obtained by the subsequent machine 50A, no measurement or test was performed.

[Examples 11 to 12]

Except for changing the raw materials as described in Table 2, the same procedure as in Example 10 was carried out to obtain granular polycarbonate. Table 2 shows the manufacturing conditions, measurement, and test results.

[Table 2]

31: Mixing tank

32, 34A, 34B: Transfer pump

33A, 33B: Dissolution mixture storage tank

35: 1st Aggregator

36: Discharge gear pump

37: 2nd aggregator

38,40,43,46A,46B,49A,49B: Supply pump

39: The first inert gas absorption device

41,47A,47B: Pressure regulating valve

42: The first guide contacts the downflow polymerization device

44: The second inert gas absorption device

45:Three-way polymer valve

48A, 48B: Second guide contact flow polymerization device

50A: Rear section machine

50B: Rear section machine

Claims (19)

A method for manufacturing polycarbonate, which includes: using dihydroxy compounds and diaryl carbonate compounds or prepolymers thereof as raw materials, flowing down along the outer surface of a guide member, and manufacturing polycarbonate by a melt polycondensation method. In the ester step, the aforementioned dihydroxy compound contains a dihydroxy compound represented by the following formula (1),

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and a cycloalkyl group with 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. . The manufacturing method of polycarbonate according to claim 1, wherein the mass ratio of the dihydroxy compound represented by formula (1) with respect to the total amount of dihydroxy compounds exceeds 0.98, and the reaction in the aforementioned melt polycondensation method The temperature exceeds 220℃ and is below 330℃. The manufacturing method of polycarbonate according to claim 1, wherein the dihydroxy compound contains an aliphatic diol compound, an alicyclic diol compound and a bisphenol compound represented by the following formula (3). One or more species in the group, HO-R ₅ -OH (3) In the formula, R ₅ represents an alkylene group having 2 to 12 carbon atoms. The manufacturing method of polycarbonate according to claim 3, wherein the mass ratio of the dihydroxy compound represented by formula (1) to the total amount of the dihydroxy compound is 0.5 or more and 0.98 or less, and the aforementioned melt polycondensation method The reaction temperature in is 170 to 220°C. The method for producing polycarbonate according to any one of claims 1 to 4, wherein the diaryl carbonate compound contains a diaryl carbonate compound obtained using carbon dioxide as a raw material. The method for producing polycarbonate according to any one of claims 1 to 4, wherein the diaryl carbonate compound contains diphenyl carbonate. The manufacturing method of polycarbonate according to any one of claims 1 to 4, wherein the dihydroxy compound represented by the aforementioned formula (1) contains isosorbide (Isosorbide), isomannitol ( Isomannide) and isoidide (Isoidide) form one or more of the group. The manufacturing method of polycarbonate according to any one of claims 1 to 4, wherein the dihydroxy compound represented by the aforementioned formula (1) contains a compound represented by the following formula (4),

The manufacturing method of polycarbonate according to any one of claims 1 to 4, wherein the melt volume flow rate (MVR: Melt Volume Flow Rate) of the obtained polycarbonate is 1.5 to 75 cm at 270°C. ³ /10min. The method for producing polycarbonate according to any one of claims 1 to 4, wherein the raw material is a raw material that has absorbed nitrogen. The manufacturing method of polycarbonate according to claim 3, wherein the aliphatic diol compound represented by the formula (3) contains a compound selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. , 1,5-pentanediol and 1,6-hexanediol. The aforesaid alicyclic diol compound contains one or more selected from the group consisting of 1,4-cyclohexanediol and 1,4-cyclohexanediol. One or more of the group consisting of hexane dimethanol. The manufacturing method of polycarbonate according to any one of claims 1 to 4, wherein the step of manufacturing the polycarbonate is performed using a guide contact flow polymerization device, and the guide contact flow polymerization device is Satisfying the following <Condition (1)> to <Condition (9)>, <Condition (1)> has: a liquid receiving port, a liquid supply area of a guide for supplying liquid to the evaporation area through the porous plate; The space surrounded by the foregoing porous plate, the side shell and the bottom shell is provided with an evaporation zone with a plurality of guides extending downward from the foregoing porous plate; a vacuum vent set in the foregoing evaporation zone; and a vacuum vent set on the bottom shell. The lowermost liquid discharge port; <Condition (2)> In the aforementioned liquid supply area, a flow path control member is provided in the aforementioned liquid supply area, and the flow path control member has: a flow path that is supplied from the aforementioned liquid receiving port to the porous plate. The function of liquid flowing from the peripheral part to the central part of the porous plate; <Condition (3)> The internal cross-sectional area A (m ² ) in the horizontal plane of the side shell of the evaporation zone satisfies the following formula (I), 0.7≦A≦300 Formula (I) <Condition (4)> The ratio of the aforementioned internal cross-sectional area A (m ² ) to the aforementioned internal cross-sectional area B (m ² ) in the horizontal plane of the liquid discharge port satisfies the following formula (II) , 20≦A/B≦1000 Formula (II) <Condition (5)> With respect to the upper side shell, the bottom shell constituting the bottom of the aforementioned evaporation zone is connected at an angle C degree in the interior, and the aforementioned angle C The degree satisfies the following formula (III), 110≦C≦165 Formula (III) <Condition (6)> The length h (cm) of the aforementioned guide satisfies the formula (IV), 150≦h≦5000 Formula (IV) <Condition (7)〉The total external surface area S (m ² ) of the plurality of aforementioned guide members satisfies the formula (V), 2≦S≦50000 Formula (V) 〈Condition (8)〉The average hole per 1 m ² of the aforementioned porous plate Number N (pieces/m ² ) satisfies the formula (VI), 50≦N≦3000 Formula (VI) 〈Condition (9)〉 The upper area T (m ² ) of the above-mentioned porous plate including the upper area of the holes of the above-mentioned porous plate , the ratio to the total effective cross-sectional area Q (m ² ) of the holes satisfies the following formula (VII), 50≦T/Q≦3000 formula (VII). A polycarbonate having a structural unit represented by the following formula (2) and a b* value of 0.7 or less,

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group having 5 to 10 ring carbon atoms. , a carbocyclic aromatic group with 5 to 10 carbon atoms in the ring, or a carbocyclic aralkyl group with 6 to 10 carbon atoms; in addition, among R ₁ , R ₂ , R ₃ , and R ₄ , more than one The hydrogen atom may be substituted by 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 or a nitro group. . The polycarbonate according to claim 13, wherein the mass ratio of the structural units represented by formula (2) relative to the total amount of polycarbonate exceeds 0.98. The polycarbonate according to claim 13, which further contains: a structural unit selected from an aliphatic diol compound represented by the following formula (5), a structural unit derived from an alicyclic diol compound, and a structural unit derived from a bisphenol. One or more types of the group of structural units of the compound, -OR ₅ -OC(O)- (5) In the formula, R ₅ represents an alkylene group having 2 to 12 carbon atoms. The polycarbonate according to claim 15, wherein the mass ratio of the structural units represented by formula (2) relative to the total amount of polycarbonate is 0.5 or more and 0.98 or less. The polycarbonate according to any one of claims 13 to 16, wherein the melt volume flow rate (MVR) is 40 cm ³ /10 min or less at 230°C. The polycarbonate according to any one of claims 13 to 16, wherein the melt volume flow rate (MVR) is 1.5 to 75cm ³ /10min at 270°C. The polycarbonate according to any one of claims 13 to 16, wherein the haze is 0.8% or less.

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