KR20200005703A - Process for preparing polycarbonate and apparatus forpreparing polycarbonate - Google Patents

Abstract

The present invention relates to an end-capped polycarbonate producing method which includes: a step of forming a polycarbonate product by melting and polymerizing an aromatic dihydroxy compound, carbonic acid diester, and optionally a catalyst in a prepolymerization container (4a/4b); a step of transferring the polycarbonate product from the prepolymerization container (4a/4b); a step of mixing the polycarbonate product with an end-capping agent at a pressure of at least about 760 mmHg under a hermetic sealing; and a step of transferring the mixture of the end-capping agent and the polycarbonate product to a subsequent polymerization container (9) and performing an end-capping of the polycarbonate product. The present invention also relates to end-capped polycarbonate producing equipment which includes: the prepolymerization container (4a/4b) having an inlet and an outlet; the subsequent polymerization container (9) having an inlet and an outlet; a mixer connected with fluid between the outlet of the prepolymerization container (4a/4b) and the inlet of the subsequent polymerization container (9); and a filling unit allowing the mixer to be filled with the end-capping agent wherein the mixer is welded and sealed at a pressure of 760 mmHg or more. The present invention is able to produce polycarbonate efficiently.

Description

PROCESS FOR PREPARING POLYCARBONATE AND APPARATUS FORPREPARING POLYCARBONATE}

Polycarbonates are widely used because of their excellent mechanical properties such as impact resistance, heat resistance and transparency.

Processes known in the art for producing sheets include, for example, interfacial processes and melting processes.

Aromatic diols, for example bisphenol A, are reacted directly with phosgene.

Transesterifying the mixture in the molten state with diallyl carbonate, such as diphenyl carbonate

Exchange is generally preferred because it does not use solvents such as phosgene or methylene chloride, which may be toxic.

It also allows for more economic production.

When the end-capping agent is used to end-cap the polycarbonate polymerized by the melting process,

It was investigated with the aim of improving color tone, heat resistance and hydrolysis resistance. For example, Japanese Patent Laid-Open No. 63-179

301 discloses a bisphenol A polycarbonate whose end is capped with methyl salicylate.

2-175723 discloses aromatic dihydrides in the presence of phenols having 1 to 40 carbon atoms such as butylphenol, cumylphenol and phenylphenol.

By polycondensing the hydroxy compound and the carboxylic acid diester, the final hydroxyl group is less than 30% and the threshold viscosity is within 03.

A process for producing a polycarbonate of 10 dl / g (at 20 ° C. in methylene chloride) is disclosed.

However, even when the end-capping agent is used, the degree of polymerization will not be high enough, and the polycondensation reaction will not progress sufficiently.

It should be noted that low molecular weight polycarbonates and / or polycarbonates having a broad molecular weight distribution will be obtained.

In addition, the efficacy of the end-capping agent may be poor even if the capping agent is added after the polycondensation reaction has progressed to the desired level.

Therefore, the time and mixing conditions of the end-capping agent added are important factors.

For this reason, Japanese Patent Application Laid-open No. Hei 10-36497 is a method for melt polycondensation of aromatic dihydroxy and diphenyl carbonate.

An improved process for producing aromatic polycarbonates is disclosed.

The short-capping agent is obtained by adding a compound of formula (1) after the intrinsic viscosity of the polycarbonate reaches 03 dl / g

International Publication No. WO / 98/47938 also discloses the end-capping agents of Formula 1 above at temperatures of 200 to 350 ° C. and 1013 hPa (760).

ratio of from 03 to 40 molar equivalents based on the hydroxy terminus of the polycarbonate under conditions of up to mm Hg)

And added for at least 01 second and kneaded, then stabilizers were added at a temperature of 200 to 350 ° C. and 1333 × 10 5 hPa (10 5 m

mHg) It is proposed to add and knead for more than 01 second at a pressure below.

In addition, Japanese Patent Application Laid-Open No. 7-90074 discloses an active diester and an acid halide after the transesterification ratio exceeds 70% or more.

By transesterification of a hydroxy compound or a carboxylic acid diester to which a hydride or divalent or higher acid anhydride is added

Disclosed is an improved process for producing polycarbonates having an increased degree of polymerization. Japanese Patent Laid-Open No. 6-157739

At Applicants Melting Aromatic Dihydroxy Compounds and Carbonic Acid Diesters in Two or More Reactors Connected in Series

Condensation, wherein an end-capping agent is added through the inlet of the one or more reactors and the viscosity of the polymer reaches 020 cc / g

Proposed improved method for producing aromatic polycarbonate by melt polycondensation

Since such patent documents disclose that practitioners in the art can determine that polycarbonate has a particular

When the degree of polymerization was reached, an experiment was carried out with the addition of end-capping agents.

Polycarbonates that do not decompose and provide improved end-capping efficacy)

There is still a need for a way to create it.

Polycars with high end-capping rates, high molecular weights and small number of hydroxyl end groups

Allows efficient production of carbonates The first stage of the process involves melt polycondensation for prepolymerisation, for example tanks.

The polycarbonate is formed by the polymerization reaction. During this prepolymerization step, the polymer has a relatively low intrinsic viscosity.

End-capping agent is not present. After prepolymerization the polymer is transferred to a subsequent polymerization vessel, for example a tank.

Add end-capping agent and mix to prevent volatilization and loss. Transfer operations include weld seals and pressures of 1013 hPa (760 mmHg).

The polycarbonate is subsequently capped in a subsequent polymerization vessel, during which the polymer has a high critical viscosity.

It is

The methods and apparatus disclosed herein are polycars having a high end-capping rate, a high molecular weight and a small number of hydroxyl end groups.

Allows efficient production of carbonates The first stage of the process involves melt polycondensation for prepolymerisation, for example tanks.

The polycarbonate is formed by the polymerization reaction. During this prepolymerization step, the polymer has a relatively low intrinsic viscosity.

End-capping agent is not present. After prepolymerization the polymer is transferred to a subsequent polymerization vessel, for example a tank.

Add end-capping agent and mix to prevent volatilization and loss. Transfer operations include weld seals and pressures of 1013 hPa (760 mmHg).

The polycarbonate is subsequently capped in a subsequent polymerization vessel, during which the polymer has a high critical viscosity.

It is

As used herein, the term 'prepolymerization' refers to the formation of a polycarbonate after which the polycarbonate terminal hydroxide

Means that the group of seals is capped. Separation of the process into two stages is a rapid and sufficient degree of

Allow for syntheses, and in subsequent polymerization stages appropriately impart the usual effect of the end-capping agent.

Significantly increases the degree of synthesis. Also, polycarbonates having enhanced characteristics such as color tone, heat resistance, resistance to heat aging, and moisture resistance can be used.

Produces

Antisulfide dihydroxy compounds for the production of polycarbonates are known, for example bisphenol of formula

Contains compound

Formula 2

Where

R a and R b may each be the same or different as a halogen atom or a monovalent hydrocarbon group,

m and n are integers from 0 to 4

X is -C (R c) (R d)-, -C (R e)-, -O-, C (O)-, -S-, -SO 2-or

R c and R d are each a hydrogen atom or a monovalent hydrocarbon group,

R c and R d may form a cyclic structure,

R e is a divalent hydrocarbon group

Specific examples of the aromatic dihydroxy compound represented by the formula (2) include bis (hydroxyaryl) alkanes such as bis (4-hydroxy

Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane ('bisphenol A'), 2,2-bis (4-

Hydroxyphenyl) butane, 2,2-bis- (4-hydroxyphenyl) octane, (bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy)

Cy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane

And 2,2- (4-hydroxy-3,5-dibromophenyl) propane; Bis (hydroxyaryl) cycloalkanes for example 1,1-bis (4-high

Hydroxyphenyl) cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane; Dihydroxyarylethers for example 4,4'-dihi

Hydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; Dihydroxydiarylsulfides for example 4,4'-di

Hydroxydiphenylsulfide and 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide

Id; And dihydroxydiarylsulfones such as 4,4'-di hydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldipe

Include, but are not limited to, nilsulfone

In addition to the aromatic dihydroxy compound of Formula 2, an aromatic dihydroxy compound of Formula 3 may also be used.

Wherein each R f is independently a hydrocarbon group having 1 to 10 carbon atoms, at least one of which is substituted with a halogen atom

Halogenated hydrocarbon or one or more halogen atoms, p is an integer from 0 to 4

Specific examples of the aromatic dihydroxy compound represented by the formula (3) include resorcinol and substituted resorcinol, such as 3-meth

Thilesorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, 3-t-butylresorcinol, 3-phenylresorcinol

, 3-cumolesorcinol, 2,3,4,6-tetrafluororesorcinol and 2,3,4,6-tetrabromoreresorcinol; Catechol; Hydroquinone

And substituted hydroquinones such as 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhigh

Droquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3

, 5,6--tetra-t-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone

Contains

2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tet of Chemical Formula 4 in addition to the aromatic dihydroxy compounds of Chemical Formulas 2 and 3

Lamethyl-1,1'-spirobi- [1H-indene] -7,7-diol may also be used.

Formula 4

The aromatic dihydroxy compounds represented by the formulas (2) to (4) may be used alone or in combination of two or more.

In addition, the melt polycondensation catalyst is individually or dihydroxy compounded to the aromatic dihydroxy compound and the carboxylic acid diester.

Water and carboxylic acid diesters may be added after mixing. The melt polycondensation catalyst may be an alkali metal compound and / or alkaline earth

Metal compounds (a) (also referred to herein as 'alkali (earth) metal compounds (a)').

Specific examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate,

Lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, li

Lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium boroha

Idride, sodium borophenylate, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogenpo

Phosphate, dipotassium hydrogenphosphate, iridium hydrogenphosphate, disodium, dipotassium and iridium of bisphenol A

Salts, and sodium, potassium and lithium salts of phenol.

Specific examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate,

Barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbon

Carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, cal

Calcium stearate, barium stearate, magnesium stearate, and strontium stearate

The melt polycondensation catalyst may additionally comprise a basic compound (b) which can be used in combination with the alkali (earth) metal compound (a).

Examples of basic compounds (b) include nitrogen-containing basic compounds which can be easily decomposed or evaporated at high temperatures.

Specific examples thereof include ammonium hydroxide containing alkyl, aryl, alkaryl groups, and the like, for example tetramethylammonium hydroxide

Id (Me 4 NOH), tetraethylammonium hydroxide (Et 4 NOH), tetrabutylammonium hydroxide (Bu 4 NOH), and trimethylbenzylammonium hydroxide {Φ-CH 2 (Me) 3 NOH [where Is a phenyl group]}; Tertiary amines

Trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine; Formula R 2 NH, wherein R is for example alkyl group

For example methyl or ethyl, or an aryl group such as phenyl or tolyl]; Formula RNH [where R is for example

Primary alkyl amines such as methyl or ethyl, or aryl groups such as phenyl or tolylida; Pyridine example

4-dimethylaminopyridine, 4-diethylaminopyridine, and 4-pyrrolidinopyridine; Imidazoles for example 2-methylimidazole

And 2-phenylimidazole; And basic salts such as ammonia, tetramethylammonium borohydride (Me 4 NBH 4), tetra

Butylammonium borohydride (Bu 4 NBH 4), tetrabutylammonium tetraphenylborate (Bu 4 NBPh 4), and tetrame

Trimethylammonium tetraphenylborate (Me 4 NBPh 4), of which tetraalkylammonium hydroxide is preferred.

All

The melt polycondensation catalyst may further comprise a boric acid compound (c), including, for example, boric acid and boric acid esters.

Examples of ters may include those represented by the following formula:

B (OR) n (hydroxyl) 3-n

Where

R is alkyl, for example methyl or ethyl, or aryl, for example phenyl,

n is an integer from 1 to 3

Specific examples of boric acid esters are trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, trihep

Butyl borate, triphenyl borate, tritolyl borate and trinaphthyl borate

The melt polycondensation catalyst is preferably a combination of an alkali (earth) metal compound (a) and a nitrogen-containing basic compound (b), and more

Preferably three classes of compounds, namely alkali (earth) metal compounds (a), nitrogen-containing basic compounds (b) and boric acid or boric acid s

It is a combination of ter (c). A combination of an alkali (earth) metal compound (a) and a nitrogen-containing basic compound (b) or an alkali (earth) metallization.

When a combination of compound (a), nitrogen-containing basic compound (b) and boric acid or boric acid ester (c) is used, the respective catalyst components

Added as a mixture to a molten mixture of bisphenols and carboxylic acid diesters or a melt blend of bisphenols and carboxylic acid diesters

Can be added separately to the compound

The end-capping agents used in the formation of end-capped polycarbonates are carbonate compounds, carboxylic acid esters, epoxy compounds

And combinations thereof, the use of carbonate compounds and / or carboxylic acid ester compounds.

Directly carbonate compounds and / or carboxylic ester compounds may be represented by the formula

Formula I

Where

R 1 is an electron selected from the group consisting of a halogen atom, a nitro group and an alkoxycarbonyl group having 1 to 30 carbon atoms

A saliva group, wherein R 1 may be linked to an arbitrary position of the benzene ring, preferably to an ortho position (o-position),

R 2 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon atoms

Is an aryloxy group of 6 to 30

n is an integer from 1 to 3

Particular examples of end-capping agents represented by Formula I are 2-chlorophenyl aryl carbonates such as 2-chlorophenyl phenyl carbonane

, 2-chlorophenyl 4'-methylphenyl carbonate, 2-chlorophenyl 4'-ethylphenyl carbonate, 2-chlorophenyl 4'-n-butylphenyl

Carbonate, 2-chlorophenyl 4'-t-butylphenyl carbonate, 2-chlorophenyl 4'-nonylphenyl carbonate, 2-chlorophenyl 4'-ku

Mill carbonate, 2-chlorophenyl naphthyl carbonate, 2-chlorophenyl 4'-methoxyphenyl carbonate, 2-chlorophenyl 4'-ethoxyphenyl carbonate, 2-chlorophenyl 4'-n-butoxyphenyl carbonate, 2 -Chlorophenyl 4'-t-butoxyphenyl carbonate, 2-cle

Lorophenyl 4'-nonyloxyphenyl carbonate, 2-chlorophenyl 4'-t-propyloxyphenyl carbonate, 2-chlorophenyl 2'-methoxycar

Carbonylphenyl carbonate, 2-chlorophenyl 4'-methoxycarbonylphenyl carbonate, 2-chlorophenyl 2'-ethoxycarbonylphenyl carbonane

, 2-chlorophenyl 4'-ethoxycarbonylphenyl carbonate, 2-chlorophenyl 2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbon

Nate and 2-chlorophenyl 2 '-(o-ethoxycarbonylphenyl) oxycarbonylphenyl carbonate; 2-chlorophenyl alkyl carbonate

2-chlorophenyl methyl carbonate, 2-chlorophenyl ethyl carbonate, 2-chlorophenyl n-butyl carbonate, 2-chloro

Phenyl octyl carbonate, 2-chlorophenyl i-propyl carbonate, 2-chlorophenyl 2-methoxycarbonylethyl carbonate, 2-chloro

Rophenyl 2-ethoxycarbonylethyl carbonate and 2-chlorophenyl 2- (o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-

Methoxy carbonyl phenyl aryl carbonates such as 2-methoxycarbonylphenyl phenyl carbonate, 2-methoxycarbonylphenyl methylfe

Neyl carbonate, 2-methoxycarbonylphenyl ethylphenyl carbonate, 2-methoxycarbonylphenyl propylphenyl carbonate, 2-methoxy

Carbonylphenyl n-butylphenyl carbonate, 2-methoxycarbonylphenyl t-butylphenyl carbonate, 2-methoxycarbonylphenyl hexylphenyl carbon

Carbonate, 2-methoxycarbonylphenyl nonylphenyl carbonate, 2-methoxycarbonylphenyl dodecylphenyl carbonate, 2-methoxycarbonyl

Phenyl hexadecylphenyl carbonate, 2-methoxycarbonylphenyl di-n-butylphenyl carbonate, 2-methoxycarbonylphenyl di-t-butylfe

Nyl carbonate, 2-methoxycarbonylphenyl dinonylphenyl carbonate, 2-methoxycarbonylphenyl cyclohexylphenyl carbonate, 2-

Methoxycarbonylphenyl naphthylphenyl carbonate, 2-methoxycarbonylphenyl biphenyl carbonate, 2-methoxycarbonylphenyl cumylphenyl

Carbonate, 2-methoxycarbonylphenyl 4'-methoxyphenyl carbonate, 2-methoxycarbonylphenyl 4'-ethoxyphenyl carbonate, 2-methoxy

Methoxycarbonylphenyl 4'-n-butoxyphenyl carbonate, 2-methoxycarbonylphenyl 4'-t-butoxyphenyl carbonate, 2-methoxycarbonylfe

Neyl 4'-nonyloxyphenyl carbonate, 2-methoxycarbonylphenyl 4'-cumyloxyphenyl carbonate, di- (2-methoxycarbonylphenyl) carbo

Nitrate, 2-methoxycarbonylphenyl 4'-methoxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl 2'-ethoxycarbonylphenyl carbonane

, 2-methoxycarbonylphenyl 4'-ethoxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl 2 '-(o-methoxycarbonylphenyl) oxycarbon

Phenylphenyl carbonate and 2-methoxycarbonylphenyl 2 '-(o-ethoxycarbonylphenyl) oxycarbonylphenyl carbonate; 2-methoxycarbonylfe

Nyl alkyl carbonates such as 2-methoxycarbonylphenyl methyl carbonate, 2-methoxycarbonylphenyl ethyl carbonate, 2-methoxy

Cycarbonylphenyl n-butyl carbonate, 2-methoxycarbonylphenyl octyl carbonate, 2-methoxycarbonylphenyl nonyl carbonate, 2-

Methoxycarbonylphenyl cetyl carbonate, 2-methoxycarbonylphenyl lauryl carbonate, 2-methoxycarbonylphenyl 2-methoxycarbonyl

Ethyl Carbonate, 2-methoxycarbonylphenyl 2-ethoxycarbonylethyl carbonate, 2-methoxycarbonylphenyl 2- (o-methoxycarbonyl

Phenyl) oxycarbonylethyl carbonate and 2-methoxycarbonylphenyl 2- (o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-

Ethoxycarbonylphenyl aryl carbonates for example 2-ethoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl methylphenyl

Carbonate, 2-ethoxycarbonylphenyl ethylphenyl carbonate, 2-ethoxycarbonylphenyl propylphenyl carbonate, 2-ethoxycarbon

Nylphenyl n-butylphenyl carbonate, 2-ethoxycarbonylphenyl t-butylphenyl carbonate, 2-ethoxycarbonylphenyl hexylphenyl carbonane

, 2-ethoxycarbonylphenyl nonylphenyl carbonate, 2-ethoxycarbonylphenyl dodecylphenyl carbonate, 2-ethoxycarbonylphenyl

Hexadecylphenyl carbonate, 2-ethoxycarbonylphenyl di-n-butylphenyl carbonate, 2-ethoxycarbonylphenyl di-t-butylphenyl carbon

Carbonate, 2-ethoxycarbonylphenyl dinonylphenyl carbonate, 2-ethoxycarbonylphenyl cyclohexylphenyl carbonate, 2-ethoxy

Cicarbonylphenyl naphthylphenyl carbonate, 2-ethoxycarbonylphenyl biphenyl carbonate, 2-ethoxycarbonylphenyl cumylphenyl carbon

Nate, 2-ethoxycarbonylphenyl 4'-methoxyphenyl carbonate, 2-ethoxycarbonylphenyl 4'-ethoxyphenyl carbonate, 2-ethoxy

Carbonylphenyl 4'-n-butoxyphenyl carbonate, 2-ethoxycarbonylphenyl 4'-t-butoxyphenyl carbonate, 2-ethoxycarbonylphenyl 4

'-Nonyloxyphenyl carbonate, 2-ethoxycarbonylphenyl 4'-cumyloxyphenyl carbonate, di- (2-ethoxycarbonylphenyl) carbonei

, 2-ethoxycarbonylphenyl 4'-methoxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl 4'-ethoxycarbonylphenyl carbonate, 2

-Ethoxycarbonylphenyl 2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate and 2-ethoxycarbonylphenyl 2'-(o-ethoxycarbon

Nilphenyl) oxycarbonylphenyl carbonate; 2-ethoxycarbonylphenyl alkyl carbonates for example 2-ethoxycarbonylphenyl methyl carbono

Nate, 2-ethoxycarbonylphenyl ethyl carbonate, 2-ethoxycarbonylphenyl n-butyl carbonate, 2-ethoxycarbonylphenyl octyl

Carbonate, 2-ethoxycarbonylphenyl 2-methoxycarbonylethyl Carbonate, 2-ethoxycarbonylphenyl 2-ethoxycarbonylethyl carbon

Nate, 2-ethoxycarbonylphenyl 2- (o-methoxycarbonylphenyl) oxycarbonylethyl carbonate and 2-ethoxycarbonylphenyl 2- (o-e)

Oxycarbonylphenyl) oxycarbonylethyl carbonate; 2-propoxycarbonylphenyl aryl carbonate; 2-propoxycarbonylphenyl alkyl

Carbonates; 2-butoxycarbonylphenyl aryl carbonate; 2-butoxycarbonylphenyl alkyl carbonate; 2-phenoxycarbonylphenyl ah

Reel carbonate; And 2-phenoxycarbonylphenyl alkyl carbonate

The end-capping agents represented by formula (I) also contain aromatic carboxylic acid 2-chlorophenyl esters such as 2-chlorophenyl benzoate

, 2-chlorophenyl 4-methylbenzoate, 2-chlorophenyl 4-ethylbenzoate, 2-chlorophenyl 4-n-butylbenzoate, 2-chloro

Rophenyl 4-t-butylbenzoate, 2-chlorophenyl 4-nonylbenzoate, 2-chlorophenyl 4-cumylbenzoate, 2-chlorophenyl 4-

n-butylbenzoate, 2-chlorophenyl 4-t-butylbenzoate, 2-chlorophenyl 4-nonylbenzoate, 2-chlorophenyl 4-cumylbene

Zoate, 2-chlorophenyl naphthoate, 2-chlorophenyl 4-methoxybenzoate, 2-chlorophenyl 4-ethoxybenzoate, 2-

Chlorophenyl 4-n-butoxybenzoate, 2-chlorophenyl 4-t-butoxybenzoate, 2-chlorophenyl 4-nonyloxybenzoate, 2

-Chlorophenyl 4-cumyloxybenzoate, 2-chlorophenyl 2-methoxycarbonylbenzoate, 2-chlorophenyl 4-methoxycarbonylbenzo

, 2-chlorophenyl 2-ethoxycarbonylbenzoate, 2-chlorophenyl 4-ethoxycarbonylbenzoate, 2-chlorophenyl 2- (o-

Methoxycarbonylphenyl) oxycarbonylbenzoate and 2-chlorophenyl 2- (o-ethoxycarbonylphenyl) oxycarbonylbenzoate; Aliphatic

Carboxylic acid 2-chlorophenyl esters such as 2-chlorophenyl acetate, 2-chlorophenyl propionate, 2-chlorofe

Nyl valerate, 2-chlorophenyl ferragonate, 2-chlorophenyl 1-methylpropionate, 2-chlorophenyl 2-methoxycarbo

Nylpropionate, 2-chlorophenyl 2-ethoxycarbonylbutyrate, 2-chlorophenyl 4 '-(2-methoxycarbonylphenyl) oxycarbonyl

Butyrate and 2-chlorophenyl 4 '-(2-ethoxycarbonylphenyl) oxycarbonyl butyrate; Aromatic carboxylic acid (2'-methoxycarbonylphenyl) esters such as (2-methoxycarbonylphenyl) benzoate, 4-methylbenzoyl- (2'-methoxycarbonylphenyl) ester, 4-ethyl

Benzoyl- (2'-methoxycarbonylphenyl) ester [sic], 4-n-butylbenzoyl- (2'-methoxycarbonyl) ester [sic], 4-t-butylbenzo

Mono- (2'-methoxycarbonyl) ester, (2'-methoxycarbonylphenyl) naphthoate, (2'-methoxycarbonylphenyl) 4-nonylbenzoate, (2

'-Methoxycarbonylphenyl) 4-cumylbenzoate, (2'-methoxycarbonylphenyl) 4-methoxybenzoate, (2'-methoxycarbonylphenyl) 4-

Oxybenzoate, (2'-methoxycarbonylphenyl) 4-n-butoxybenzoate, (2'-methoxycarbonylphenyl) 4-t-butoxybenzoate, (2 '

-Methoxycarbonylphenyl) 4-cumyloxybenzoate, (2'-methoxycarbonylphenyl) 2-methoxycarbonylbenzoate, (2'-methoxycarbonyl

Phenyl) 4-methoxycarbonylbenzoate, (2'-methoxycarbonylphenyl) 4-ethoxycarbonylbenzoate, (2'-methoxycarbonylphenyl) 3- (o

-Methoxycarbonylphenyl) oxycarbonylbenzoate, (2'-methoxycarbonylphenyl) 4- (o-methoxycarbonylphenyl) oxycarbonylbenzoate

And (2'-methoxycarbonylphenyl) 3- (o-ethoxycarbonylphenyl) oxycarbonylbenzoate; Aliphatic carboxylic acid (2'-methoxycarbonylphenyl)

Esters such as (2'-methoxycarbonylphenyl) stearate; Aromatic carboxylic acid (2'-ethoxycarbonylphenyl) esters

For example, (2'-ethoxycarbonylphenyl) benzoate, 4-methylbenzoyl- (2'-ethoxycarbonylphenyl) ester [sic], 4-ethylbenzoyl- (2'-

Ethoxycarbonylphenyl) ester [sic], 4-n-butylbenzoyl- (2'-ethoxycarbonylphenyl) ester [sic], 4-t-butylbenzoyl- (2'-

Ethoxycarbonylphenyl) ester, (2'-ethoxycarbonylphenyl) naphthoate, (2'-ethoxycarbonylphenyl) 4-nonylbenzoate, (2'-

Ethoxycarbonylphenyl) 4-cumylbenzoate, (2'-ethoxycarbonylphenyl) 4-methoxybenzoate, (2'-ethoxycarbonylphenyl) 4-ethoxy

Cybenzoate, (2'-ethoxycarbonylphenyl) 4-n-butoxybenzoate, (2'-ethoxycarbonylphenyl) 4-t-butoxybenzoate, (2'-

Ethoxycarbonylphenyl) 4-nonyloxybenzoate, (2'-ethoxycarbonylphenyl) 4-cumyloxybenzoate, (2'-ethoxycarbonylphenyl) 2

-Methoxycarbonylbenzoate, (2'-ethoxycarbonylphenyl) 4-ethoxycarbonylbenzoate, (2'-ethoxycarbonylphenyl) 3- (o-methoxy

Carbonyl) oxycarbonylbenzoate, (2'-ethoxycarbonylphenyl) 4- (o-methoxycarbonylphenyl) oxycarbonylbenzoate and (2'-ethoxy

Carbonylphenyl) 3-o-methoxycarbonylphenyloxycarbonylbenzoate; Aliphatic carboxylic acid (2'-ethoxycarbonylphenyl) esters

For example (2'-ethoxycarbonylphenyl) stearate; Aromatic carboxylic acid (2-propoxycarbonylphenyl) esters; Aliphatic carboxylic acid (2 '

Propoxycarbonylphenyl) esters; Aromatic carboxylic acid (2'butoxycarbonylphenyl) esters; Aliphatic carboxylic acid (2-butoxycarbo

Nylphenyl) esters; Aromatic carboxylic acid (2'-phenoxycarbonylphenyl) esters; And aliphatic carboxylic acids (2'phenoxycarbonylphenyl) s

We include ter

In addition, the carbonate compounds and / or carboxylic ester compounds represented by the following formula (II) may also be used as end-capping agents.

have

Formula II

Wherein R 3 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms

Or an aryloxy group having 6 to 30 carbon atoms. When R 3 is an aryloxy group having 6 to 30 carbon atoms, the compound is an electron sphere.

It does not contain tough groups such as halogen atoms, nitro groups or alkoxycarbonyls

Particular examples of end-capping agents represented by formula (II) include phenyl aryl carbonates such as diphenyl carbonate, phenyl 4'-methylphene

Neyl carbonate, phenyl 4'-ethylphenyl carbonate, phenyl 4'-n-butylphenyl carbonate, phenyl 4'-t-butylphenyl carbonate, pe

Neyl 4'-nonylphenyl carbonate, phenyl 4'-cumylphenyl carbonate, phenyl naphthyl carbonate, phenyl 4'-methoxyphenyl carbonate,

Phenyl 4'-ethoxyphenyl carbonate, phenyl 4'-n-butoxyphenyl carbonate, phenyl 4'-t-butoxyphenyl carbonate, phenyl 4'-furnace

Nyloxyphenyl carbonate and phenyl 4'-t-propyloxyphenyl carbonate; And phenyl alkyl carbonates for example phenyl methyl car

Carbonate, phenyl ethyl carbonate, phenyl n-butyl carbonate, phenyl octyl carbonate and phenyl i-propyl carbonate

Should

Further examples of compounds represented by formula (II) which can be used as end-capping agents include aromatic carboxylic acid phenyl esters, for example

Phenyl benzoate, phenyl 4-methylbenzoate, phenyl 4-ethylbenzoate, phenyl 4-n-butylbenzoate, phenyl 4-t-butylbene

Zoate, Phenyl 4-nonylbenzoate, Phenyl 4-cumylbenzoate, Phenyl naphthoate 4-phenyl methoxybenzoate, Phenyl 4-

Ethoxybenzoate, phenyl 4-n-butoxybenzoate, phenyl 4-t-butoxybenzoate, phenyl 4-nonyloxybenzoate and phenyl

4-cumyloxybenzoate; And aliphatic carboxylic acid phenyl esters such as phenyl acetate, phenyl propionate, phenyl

Valerate, phenyl ferragonate, phenyl 1-methylpropionate and phenyl stearate

An exemplary process and apparatus is shown in FIG. 1, which comprises a feedstock stirrer tank 1, feedstock drums 2a and 2b,

Pipes 3a, 3b, 3c and 6, prepolymerization vessels 4a and 4b, blowoff pipes 5a, 5b and 5c, end-capping agent drum 7, fixed mixer 8,

And a subsequent polymerization vessel (9). The feedstock for polycarbonate polycondensation in the process is mixed in a feedstock stirrer tank (1).

The stirrer tank 1 has an agitator blade on the vertical axis of rotation. The feedstock drums 2a and 2b are filled with an aromatic dihydroxy compound and a carboxylic acid diester, respectively. Each feedstock

From the drums 2a and 2b through the pipes 3a and 3b to the feedstock stirrer tank 1 continuously.

The agitator tank 1 may be purged with nitrogen gas since it is preferable that there is substantially no oxygen in the atmosphere.

In order to form a homogeneous solution containing an aromatic dihydroxy compound and a carboxylic acid diester, a plurality of stirrer tanks 1

Can be arranged in series

The melt polycondensation catalyst is added to the stirrer tank 1 by a pump (not shown) or one of the feedstock drums 2a and 2b.

To either or both, in which case the melt polycondensation catalyst is also supplied from the feedstock drums 2a and / or 2b to the pipes 3a and / or 3

continuously fed via b) The alkali (earth) metal compound (a) is from 1 × 10 -8 to 1 × 10 -3 moles per mole of bisphenol, preferably

Crab during the melt polycondensation reaction in an amount of 1 × 10 −7 to 2 × 10 −6 moles, more preferably 1 × 10 −7 to 8 × 10 −7 moles

It is preferable to include alkali (earth) metal compounds (a) already present in the bisphenol feedstock for the polycondensation reaction.

The amount of alkali (earth) metal compound (a) to be added so that the amount present in the polycondensation reaction per mole of bisphenol falls within the above range.

It is preferable to limit the nitrogen-containing salts when the nitrogen-containing basic compound (b) is combined with the alkali (earth) metal compound (a)

The basic compound (b) is contained in an amount of 1 × 10 −6 to 1 × 10 −1 mole, preferably 10 × 10 −5 to 10 × 10 −2 mole per mole of bisphenol.

This amount is sufficient to produce a high molecular weight polycarbonate product and a high level of polymerization activity.

It is preferable because the polycondensation reaction proceeds. The boric acid compound (c) is a mole of boric acid or boric acid ester per mole of bisphenol.

When indicated, 1 × 10 −8 to 1 × 10 −1 mole, preferably 1 × 10 −7 to 1 × 10 −2 mole, more particularly preferably 10

Can be used in amounts of × 10 -6 to 1 × 10 -4 moles

In FIG. 1, the initial melt polycondensation of the mixed feedstocks is performed by pumping the mixed feedstocks (not shown) into the pipe 3.

It begins by feeding to prepolymerization vessels 4a and 4b through c). Premixing vessels 4a and 4b have mixing blades having a vertical axis.

Decompression is maintained by the blowoff pipes 5a and 5b provided on the prepolymerization vessels 4a and 4b.

Some of the reaction monomers can be fractionated, wherein phenol is removed from the system and the less monomers are prepolymerized (4a and

Also, the molten polycondensation catalyst may be supplied to the prepolymerization vessels 4a and 4b.

Prepolymerization vessels 4a and 4b may be used as shown in FIG. 1 or a single stage prepolymerization vessel may be used.

B, 2 to 4 steps are preferred.

The reaction temperature in the first prepolymerization vessel 4a is preferably 50 to 270 ° C, more preferably 150 to 260 ° C.

Is 6 mmHg (8 mbar) from atmospheric pressure, preferably from 400 mmHg to 6 mmHg (053 mbar to 8 mbar), more

Preferably from 300 mmHg to 6 mmHg (from 040 mbar to 8 mbar). In the second prepolymerization vessel 4b

The reaction temperature is usually 160 to 300 ° C, preferably 200 to 280 ° C. The pressure is 1 to 50mmHg, preferably

Is 1 to 30 mmHg. If there are more than two stages, the pressure is preferably lowered and the temperature is within the above range.

It is desirable to raise in each successive stage.

The aromatic polycarbonate reaction product in the prepolymerization vessels 4a and 4b is 005 to 05 dl / g, preferably 010 to 04

5 kV / g, more preferably has a threshold viscosity [η] (at 20 ° C. in methylene chloride) of 010 to 04 kV / g.

After reaching the viscosity value, the polycarbonate is removed from the prepolymerization vessel (s) and ultimately fed to the subsequent polymerization vessel (9).

However, before reaching the subsequent polymerization vessel 9, the polycarbonate is mixed with the end-capping agent.

It may take place in a vessel (not shown), but most conveniently in the piping 6 connecting the prepolymerization vessel and the subsequent polymerization vessel.

Stand up

As shown in FIG. 1, the end-capping agent is preferably returned to tubing 6 through tubing 3c by means of a pump (not shown).

The end-capping agent and the polycarbonate product are mixed.

Preheated in feedstock drum 7 and introduced into tubing 6 through tubing 3c. End-capping agents as mentioned herein

Preferably from 05 to 20 moles, more preferably from 07 to 15 moles, in particular per polycarbonate terminated hydroxyl group equivalent

Preferably it is used in the ratio of 08-12 mol.

In order to mix the end-capping agent and the polycarbonate, fixation as shown in FIG. 2 inside the tubing 6 shown in FIG.

It is desirable to provide a mixer wherein two or more fixed mixers can be arranged in series. Fixed mixers that can be used.

Examples of are described, for example, in Japanese Patent Application Laid-Open No. Hei 5-131126 and Japanese Patent No. Hei 9-506318.

This is a perspective view of the preferred fixed mixer 10. This fixed mixer 10 is a first guide plate array 11 and a second guide plate array (

Contains 12)

As shown in FIG. 2, the first guide plate array 11 has two or more triangular first guide plates arranged circumferentially.

The induction plate is located at the upstream end of the fixed mixer 10 with respect to the fluid flow direction. In addition, each of the first induction plates has a pipe 6.

Down connected near the central axis (not shown) of the piping 6 from the base, which is firmly attached to the inner wall (not shown) of the

The second guide plate array 12 is equally triangular as the first guide plate array 11. The second guide plate array 12 is inclined at an apex at the stream end.

Each of the second guide plates has a vertex near the center axis connected to the inside of the first guide plate array 11.

Is inclined toward the base which is firmly attached to the inner wall (not shown) of the tubing 6 at the downstream end from the circumference of the first guide plate array 11. Spaced apart

If polycarbonate and end-capping agent flowing through tubing 6 (not shown) pass through stationary mixer 10, the tubing (

6) the periphery of the polycarbonate product and end-capping agent flowing near the inner wall of (not shown)

From the center of the pipe 6 (not shown), respectively.

The central portion of the polycarbonate product and the end-capping agent flowing through the portion is each inclined second guide plate array 12

Is induced from the region of the central axis to the periphery region. Thus, the polycar flowing through the pipe 6 (not shown)

The carbonate product and the end-capping agent are mixed by switching the points around the circumference and center of the flow

However, the fixed mixer is not limited to that illustrated in FIG. 2, for example, may be as illustrated in FIG. 3.

The fixed mixer illustrated in FIG. 3 has two types of mixing elements 21 and 22 for mixing the polycarbonate product with the end-capping agent.

The mixing element 21, which is a 180 ° twisted rectangular plate, divides the fluid into two and imparts a rightward rotation to the fluid (

For example a mixing element that rotates the fluid to the right around the central axis of the tubing 6.

At a 180 ° twisting element 22 divides the fluid in two, imparting leftward rotation to the fluid (e.g.,

6) is a mixing element which rotates in a left direction around the central axis of the mixing element 21 and a left rotation

Mixing elements 22 for transfer are provided in alternating arrangements, each arranged to rotate 90 ° with respect to the preceding element.

With this fixed mixer, the polycarbonate product and the end-capping agent are split in two and the mixing

Twisted to the right by the small 21 and split and twisted to the left by the mixing element 22 for leftward rotation.

The fluid is mixed by repetition of the dividing and twisting action

Another preferred mixer for mixing the polycarbonate product with the end-capping agent is a prepolymerization vessel followed by a subsequent polymerization vessel.

It includes a weld-sealed mixed drum that may be provided in the middle of the piping to be joined.

Controlling evaporation and vaporization results in more efficient use of end-capping agents. Also, fewer hydroxyl termini

High molecular weight polycarbonates having groups such as molecular weights of about 8,820 to 9,540 and high of about 505 to about 610 ppm

Polycarbonates with hydroxyl end groups can be prepared.

The time at which the mixture is mixed is preferably determined by the reactivity and physical properties of the end-capping agent.

Carbonate compounds and / or carboxylic ester compounds, such as formula I, which boil in the subsequent polymerization vessel (eg 240 ° C.)

2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl boiling at above temperatures and pressures up to 20 mmHg

Phenyl carbonate), the mixing time is 30 seconds or more and 10 minutes or less, preferably 1 to 7 minutes.

End-capping reactions when end-capping agents of Formula I are used that react relatively quickly and easily with the hydroxyl end groups

Proceeds slowly. As molecular weight decrease of polycarbonate caused by excessive reaction (ester exchange reaction) is controlled,

The reaction results in a high molecular weight polycarbonate. Also under these reactions, the end-capping agent may

Paper is mixed with the paper and there is little loss of added end-capping agent under the high temperature, high vacuum conditions of the subsequent polymerization vessel (9).

Carbonate compounds and / or carboxylic ester compounds represented by the formula (II) in which the end-capping agent is boiled in the subsequent polymerization vessel.

In the case of water (for example diphenyl carbonate and phenyl p-cumyl carbonate) the mixing time in the piping 6 is at least 10 minutes, preferably

Preferably between 15 and 60 minutes. Thus, the end-capping agent represented by Formula II, wherein the end-capping agent has an electron withdrawing group

Reaction is slower than using, for example, an end-capping agent represented by formula (I).

The end-capping agent reaction proceeds slowly because sufficient residence time is provided, and the end-capping agent is homogeneous with polycarbonate.

As a result, no significant reduction in molecular weight occurs and the addition of the polymer at the high temperature and high vacuum conditions of the subsequent polymerization vessel

No loss of end-capping agent

As shown in FIG. 1, after the end-capping agent is mixed with the polycarbonate product, the mixture is fed to the subsequent polymerization vessel 9.

The reaction temperature in the subsequent polymerization vessel 9 is usually 320 ° C, preferably 250 to 310 ° C, and the pressure is 20 mmHg or less.

, Preferably 10 mmHg or less The terminal end capping agent of the polycarbonate product reacts with the polycar

The ends of the carbonate are capped in the subsequent polymerization vessel 9 to form end-capped polycarbonates.

The phenols and other by-products are provided in the subsequent polymerization vessel 9 so that end-capping can be carried out quickly and with a high level of efficiency.

Distilled off by the blowing pipe 5c

After formation of the end-capped polycarbonate, a viscous powder from the base of the prepolymerization vessel, for example using a gear pump

Remove the short-capped polycarbonate The end-capped polycarbonate is preferably 20 in methylene chloride

When measured at ℃ 020 to 10 dl / g, preferably 025 to 09 dl / g, more preferably of 030 to 08 dl / g

Has a threshold viscosity [η]

The end-capped polycarbonate is then typically extruded and pelletized with a pKa value of 3 or less as desired.

Adding sulfur-containing acidic compounds or derivatives thereof (C), ester group-containing alcohol compounds (D) and / or water (E) in phosphorous acid (B)

The phosphorous acid (B) may be in the form of a salt such as a sodium or potassium salt. The phosphorous acid (B) may be end-capped.

Based on the polycarbonate composition (A), and should be formulated in an amount of 01 to 10 ppm, preferably 02 to 5 ppm. Examples are sulfurous acid, sulfuric acid,

Sulfinic acid compounds, sulfonic acid compounds, and derivatives thereof. The ester group-containing alcohol compound (G) has 10 to 2 carbon atoms.

Partial esters and polyhydric alcohols derived from divalent fatty acids of 2 are examples of monovalent fatty acids having 10 to 22 carbon atoms.

Myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and sulfurized fish oils; And polyhydric alcohols such as ethylene glycol, gly

Cerols and pentaerythritol. These partial esters may be used alone or in mixtures.

The additives (B) to (E) are added to the end-capped polycarbonate (A) while the end-capped polycarbonate (A) is melted.

In addition, at least one compound (F) selected from phosphorus ester or trimethyl phosphate in addition to the above (B) to (E)

This component (F) is preferably 10 to 1,000 ppm based on the end-capped polycarbonate (A),

More preferably in an amount of 10 to 500 ppm

Polycarbonates (A) and additives (B) to (E) are conventional kneaders such as single screw extruders, twin screw extruders or

May be kneaded in a fixed mixer The kneader may or may not be ejected

Withholding the endcapping agent from the prepolymerization step at the point where the polymer has a relatively low threshold viscosity

After the end-capping agent is added in the welded tubing, during the subsequent polymerization step, the polymer has a relatively high critical viscosity.

By capping the ends of the polycarbonate, rapid and sufficient polymerization in the prepolymerization stage can be carried out and subsequent polymerization

The effect of the end-capping agent can be imparted to the step, thereby increasing the effect of the end-capping agent being used, resulting in an aromatic poly

Can significantly increase the degree of polymerization of carbonates. Additionally, the color, heat resistance and thermal properties of the resulting aromatic polycarbonate

Significantly enhanced effects such as resistance to aging and water resistance

The apparatus for producing end-capped polycarbonates comprises at least two reactors comprising a prepolymerization vessel and a subsequent polymerization vessel.

Characterized in that the pipes are connected in series by pipes, the pipes being filled with end-capping agent in the welded seal.

In addition, the apparatus can be used to mix end-capping agents and polycarbonate products in the piping.

Providing a fixed mixer for

Fig. 1 schematically shows such a device. Fig. 1 shows the feedstock drums 2a and 2b and the ejection pipes 5a and 5b.

With a fed feed stirrer tank 1, prepolymerization tanks 4a and 4b with ejection pipes 5a and 5b, and a fixed mixer 8

A device is shown comprising a tubing 6, an end-capping agent drum 7, and a subsequent polymerization tank 9 equipped with a blowoff pipe 5c.

The apparatus is connected to pipes 3a and 2 from feedstock drums 2a and 2b filled with aromatic dihydroxy compounds and carbonic acid diesters.

3b) can be arranged to be continuously fed to each of the feedstock stirrer tanks 1 through each feedstock stirrer tank 1

Has a stirrer blade (not shown) installed on a vertical axis (not shown) to enable mixing of the feedstock by stirring

 The mixed feedstock is prepolymerized tanks 4a and 4b through piping 3c by a pump (not shown) applied to melt polycondensation.

These prepolymerization tanks 4a and 4b are provided with agitator blades (not shown) having a vertical axis of rotation (not shown).

Pressure reduction is maintained in the prepolymerization tank by means of blowoff pipes 5a and 5b provided at the top of the tank.

The size may be multi-stage composed of two or more stages or single single, as shown in FIG.

This is preferred. The reaction mixture is fed to the subsequent polymerization tank 9 by a pump (not shown) via piping 6.

The apparatus may also comprise a fixed mixer as shown in FIGS. 2 and 3. The mixer preferably comprises polycarbonate.

And end-capping agent is provided to the tubing 6 as shown in FIGS. 1 and 3 such that it is mixed in the path to the subsequent polymerization tank.

And as an alternative to the static mixer shown in FIG. 3, the apparatus is welded to mix the end-capping agent and the polycarbonate product.

It may include a sealed mixing drum, which may be provided in the middle along the piping.

After the end-capping agent and the polycarbonate product have been introduced, the mixture is fed to a subsequent polymerization tank (9).

Directly horizontal stirrer tanks typically used in subsequent polymerization processes, ie high viscosity liquids with one or more horizontal axes of rotation

Is a horizontal processing apparatus for which one or more combinations of two or more stirrer blades are provided on the horizontal axis,

Half, wheel, paddle, rod or window frame stirrer blades and two or more stages are provided for each axis of rotation.

Thoroughly comb or diffuse the solution and continue to expose the new portion of the reaction solution.

Decompression is maintained by the supplied blowoff pipe 5c.

Rapid and sufficient polymerization in the prepolymerization step by means of the production of end-capped polycarbonates disclosed herein

To a sufficient degree and impart the usual effect of the end-capping agent in the subsequent polymerization step.

Aromatic polycarbonates having improved color tone, heat resistance, resistance to thermal aging and water resistance without sacrificing degree of polymerization

Additionally, polycarbonates having a small number of hydroxyl end groups via means of the devices and processes disclosed herein.

Nitrates can be produced efficiently In addition, the volatilization of the end-capping agent is reduced in subsequent reactors without sacrificing molecular weight

The drawings illustrating the reaction process and apparatus are for illustration only, and the disclosure is not limited thereto.

Moreover, although the present disclosure is described in detail by the following examples, the disclosure is not limited to such examples.

Example

Physical properties of the polycarbonate were evaluated as follows.

Number average molecular weight (Mn) was measured by gel permeation chromatography (GPC).

To determine the final hydroxyl group concentration, 04 g of the polycarbonate obtained was dissolved in 3 ml of chloroform.

Dissolve and terminate using a carbon nuclear magnetic resonance apparatus (13 C-NMR) (Nihon Denshi Kabushiki Kaisha GX-270) at 40 ° C.

The amount of sex hydroxyl group and chain termination group was measured

The end-capping rate is calculated from the total number of end groups and the number of chain end groups measured using 13 C-NMR as follows.

Was

End-capping rate = (number of chain end groups / total number of end groups) × 100

First, a blank polycarbonate sample was prepared for use in both Examples and Comparative Examples.

An apparatus with one stirrer tank, two prepolymerization tanks and two horizontal polymerization (subsequent polymerization) tanks was used for the polymerization.

The reaction conditions in the polymerization tanks are shown in Table 1 below. The molten bisphenol A (feed rate: 360 kg / h) transported via pipes directly from the bisphenol A production unit, and directly from distillation.

Molten diphenyl carbonate (DPC; feed rate: 355 kg / h) transported via pipe, tetraammonium hydroxide per mol of bisphenol A

25 × 10 −4 mol of TMAH, and 1 × 10 −6 mol of sodium hydroxide (NaOH) per mol of bisphenol A were maintained at this temperature.

The mixture was fed continuously to the semi-annual tank. The mixture was fed into prepolymerization tank I, prepolymerization tank II, horizontal stirrer tank (subsequent polymerization tank) I and

Sequentially feed to horizontal stirrer polymerization tank II at a feed rate of 360 kg / h of bisphenol A to conduct polymerization under the conditions described above.

Blank polycarbonate was prepared.

Physical properties of the blank polycarbonate are shown in Table 2. Weld-sealed in the formation of end-capped polycarbonate

In order to measure the effect of the mixing drum and the properties of the polycarbonate, Examples 1 and 2 are equipped with a stirrer and a pressure drop device.

Collect 127 g of blank polycarbonate obtained as described in Example 1 in a combined 300 ml volumetric vertical polymerization apparatus.

The polycarbonate was then completely melted at 300 ° C. over 25 minutes, followed by diphenyl car

Carbonate (DPC) end-capping agent was added in the amounts shown in Table 2 and for the time shown in Table 2, for example Example 1 was 10 minutes,

Example 2 was premixed by stirring at a rate of 250 rpm in a hermetically sealed state for 1 minute, and then the reaction product was 1 t.

Further reaction for 20 minutes at a pressure of orr and distillation yielded a capped polycarbonate.

Comparative Example A was operated in the same manner as in Examples 1 and 2 except that premixing in a welded hermetic state was not performed.

Comparative Example B was prepared by adding the end-capping agent and then premixing in an open state (at a normal

Obtained in the same manner as in Examples 1 and 2 except that

The effect of the weld hermetic mixing drum is shown in Table 2 below. As shown in Table 2, the effective end-capping agent utilization was extremely low when the reaction was carried out without mixing.

In Example A, the effective end-capping agent utilization was at least about 35% of the utilization measured in Example 1 and in Example 2

Only about 63% or more of the defined utilization. The reaction (ester exchange) between the end-capping agent and the polymer was excessive and

The self-weight was reduced by at least about 20% in the open system (Comparative Example 2) compared to Example 1, compared to Example 2

There was a decrease of about 28% in the voice. Thus, these data indicate that the end-capping agent is mixed with the polycarbonate.

The data indicate that the capping process is more efficient by enhancing the utilization of the agent.

Shows that higher molecular weight polycarbonates can be efficiently obtained when mixed in a weld-sealed environment

Control 1 (uncapped poles) to determine the effect of a fixed mixer on the formation and properties of end-capped polycarbonate

Licarbonate) using a polymerization apparatus equipped with two stationary mixers 8 arranged in an array of tubing 6 as shown in FIG.

Formed by melt polycondensation. The fixed mixer 8 used was the type shown in FIG.

Continuous feeding of silver feedstock DPC and bisphenol A to the monomer stirrer tank (1) at a molar ratio of 108: 1 and a mixing rate of 3 kg / h

Additionally, 25 x 10 -4 mol TMAH and 1 x 10 -6 mol sodium hydroxide per mol of bisphenol A

Cerium (NaOH) was added as a catalyst to the monomer stirrer tank 1, and then by-product phenol was removed from each of the reactors 4a, 4b and 9.

The reaction mixture was removed from the monomer stirrer tank (1) while continuously removed (step-1 vertical reactor (4a), step-2 vertical reactor (4)

b) and step-3 continuous melt polycondensation by continuous feeding to the horizontal reactor 9 to obtain a polycarbonate

Was

Formation of end-capped polycarbonates of Examples 3-9, and polycarbonate and end-capping agent mixed in tubing 6

Examples 3 to 9 (end-capping as described in Control 1 except for the use of end-capping agents at premixing times).

Polycarbonate). The end-capping agents and premix times are shown in Table 3, the abbreviations of

Used in the same sense

Comparative Example C was prepared in the same manner as in Example 3 except that the end-capping agent was added without providing a fixed mixer.

Was

The effect of the fixed mixer is shown in Table 3 * Effective end-capping agent utilization (%) = mole reduction in hydroxyl group / moles of charged end-capping agent

As shown in Table 3, when the reaction is carried out without mixing with a fixed mixer, the effective end-capping agent utilization is

Extremely low For example, in Comparative Example C, the effective utilization of the end-capping agent is only about 25% or more of the ratio measured in Example 3

In addition, the number of terminal hydroxyl groups still remaining in Comparative Example C is equivalent to the terminal hydroxyl groups remaining in Example 3

Is greater than about 120 times the number of groups. Thus, the data were used to form capped polycarbonate using a fixed mixer.

Make the capping process more effective by creating more effective utilization of end-capping agents.

While the present invention has been described with reference to exemplary embodiments, those skilled in the art will appreciate that the art can be found without departing from the scope of the invention.

Species changes can be made and equivalence can replace those elements. Also, many variations are outside the essential scope of the invention.

It may be practiced without these specific circumstances or materials to apply the teachings of the present invention.

It is intended that the invention be limited to the specific embodiments disclosed as the best mode contemplated, and that the invention be limited to all aspects falling within the scope of the appended claims.

Should be interpreted to include

Claims (1)

Aromatic dihydroxy compounds, carbonic acid diesters and optionally catalysts are melted and polymerized in a prepolymerization vessel (4a / 4b).
Forming a ricarbonate product;
Transferring the polycarbonate product from the prepolymerization vessel (4a / 4b);
The polycarbonate product is mixed with an end-capping agent at a pressure of about 760 mmHg or more under a hermetic seal.
The step; And
Transfer the polycarbonate product and end-capping agent mixture to the subsequent polymerization vessel (9) to endcap the polycarbonate product
Including pinging,
Method of Making End-capped Polycarbonates

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