JP2000128977A - Production of aromatic polycarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polycarbonate having an excellent color hue by the fusion condensation polymerization using a carbonate diester as a raw material. SOLUTION: A method is provided for producing an aromatic polycarbonate by the fusion condensation polymerization between a dihydroxy compound containing, as a main component, 2,2-bis(4-hydroxyphenyl)propane and an aromatic carbonate ester containing, as a main component, diphenyl carbonate in the presence of a basic ester exchanging catalyst, wherein 2,2-bis(4- hydroxyphenyl)propane has an ortho rhombic crystal structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polycarbonate having a good color tone.
The present invention relates to a method for producing an aromatic polycarbonate having a good color tone by using 2,2-bis (4-hydroxyphenyl) propane having a specific crystal structure.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent optical properties, electrical properties, and dimensional stability, and are self-extinguishing.
In addition, it has excellent mechanical properties such as impact resistance, and also has excellent properties such as heat resistance and transparency. Therefore, it is widely used in a wide range of applications.

[0003] As a method for producing such a polycarbonate resin, a method of directly reacting phosgene with an aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane: (interfacial polymerization method); −
Method for transesterifying an aromatic dihydroxy compound such as bis (4-hydroxyphenyl) propane with an aromatic carbonate such as diphenyl carbonate in a molten state:
(Melting method) and the like are known.

Among such production methods, a method based on a transesterification reaction (melting method) between an aromatic dihydroxy compound and a carbonic acid diester uses a toxic halogen compound such as phosgene or methylene chloride as a solvent compared with the interfacial polymerization method. There is no problem of using polycarbonate, and there is an advantage that polycarbonate can be produced at low cost, and it is considered that it is promising in the future.

[0005] In the method of producing a melt polycarbonate by transesterification, a transesterification catalyst, particularly a basic transesterification catalyst, is usually used in order to increase the production efficiency. Plastic Materials Course 17 Polycarbonate Pages 48-53 Nikkan Kogyo Shimbun Toshihisa Tachikawa, Shoichi Sakajiri

[0006] Among these transesterification catalysts, a catalyst system using a basic nitrogen compound or a basic phosphorus compound in combination with an alkali metal compound has good polycarbonate productivity and physical properties such as color tone of the obtained polycarbonate. Is preferable, since there is little generation of a branched structure in the polymer molecule and the polycarbonate has good physical properties such as melt fluidity.

[0007]

However, since the melt-polymerized polycarbonate uses an alkali metal compound and / or another metal compound as a transesterification catalyst, and further performs melt polycondensation under a high temperature condition, the The color tone is stronger than that produced by the interfacial polymerization method, and there is a problem in selling it as a product. In order to solve this problem, studies have been made from many viewpoints such as catalysts, reaction methods, reactor materials, impurities in raw materials, and the like, but no satisfactory solution has yet been found.

[0008]

Means for Solving the Problems The present inventors have been studying catalysts, reactor materials, reaction conditions, raw material impurities, and various stabilizers in order to improve the color tone of polycarbonate produced by a melt polymerization method. However, by using a specific amount of a catalyst in a specific catalyst system and using a material having an orthorhombic crystal structure as 2,2-bis (4-hydroxyphenyl) propane as a raw material, the color tone of the polycarbonate is improved. The present inventors have found that the product can be improved until it can be commercialized, and arrived at the present invention.

That is, the transesterification catalyst is a catalyst containing (A) a basic nitrogen compound or a basic phosphorus compound, and (A) an alkali metal compound, and (A) a basic nitrogen compound or a basic phosphorus compound 10-500 per mole of 2-bis (4-hydroxyphenyl) propane
Micromoles, (a) using an alkali metal compound as an alkali metal element in an amount of 0.01 to 5 microequivalents per mole of 2,2-bis (4-hydroxyphenyl) propane, and (c) starting material 2,2-bis ( By using 4-hydroxyphenyl) propane having an orthorhombic crystal structure, it has been found that the color tone of a polycarbonate produced by a melt polymerization method can be improved until it can be commercialized.

The polycarbonate used in the present invention comprises an aromatic dihydroxy compound, ie, 2,2-bis (4-hydroxyphenyl) propane and an aromatic carbonate, ie, diphenyl carbonate, as main raw materials. The unit is the main component.

[0011]

Embedded image

In the present invention, the crystal structure of the 2,2-bis (4-hydroxyphenyl) propane is known to be orthorhombic or monoclinic. As a result of examining the relationship between these crystal systems of 2-bis (4-hydroxyphenyl) propane and the color tone of a melt-polymerized polycarbonate using a specific catalyst system, it was found that the crystal form belongs to the orthorhombic system. It was found that when bis (4-hydroxyphenyl) propane was used, the color tone of the obtained polycarbonate was good.

When orthorhombic 2,2-bis (4-hydroxyphenyl) propane is used, the clear reason why the color tone of the polymer becomes good is unknown, but the present inventors adsorb impurities in the crystal. It is presumed that there is a difference in the surface activities to be performed.

As a method of obtaining orthorhombic 2,2-bis (4-hydroxyphenyl) propane, for example, a method of purifying 2,2-bis (4-hydroxyphenyl) propane by fractional melt crystallization, After obtaining a crystal adduct of 2,2-bis (4-hydroxyphenyl) propane, the crystal adduct is decomposed and purified.

In the present invention, in addition to the above 2,2-bis (4-hydroxyphenyl) propane, a small amount of an aliphatic or aromatic dihydroxy compound, dicarboxylic acid, or oxyacid which may have a substituent may be used. For the purpose of controlling the glass transition temperature, or controlling the optical properties such as improving the fluidity, increasing the refractive index, or reducing the birefringence, one or two kinds of monomers may be used as needed. It goes without saying that more than one species can be contained.

As such aromatic dihydroxy compounds, specifically, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-) Methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5
-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 4,
4'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4- Examples include dihydroxy-3-methylbenzene, bis (4-hydroxyphenyl) sulfide, and bis (4-hydroxyphenyl) sulfoxide.

Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,4-butanediol, 1,4
-Cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,10-decanediol, diethylene glycol, tetraethylene glycol, polyethylene glycol, polytetramethylene glycol and the like.

Examples of the dicarboxylic acids include succinic acid, isophthalic acid, 2,6-naphthalenedicaubonic acid,
Adipic acid, cyclohexanedicarboxylic acid, terephthalic acid, and oxyacids include, for example, p-hydroxybenzoic acid, 6-hydroxy-2 naphthoic acid, lactic acid, and the like.

Specific examples of the aromatic carbonate include, in addition to diphenyl carbonate, ditolyl carbonate, bis (2-chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, and bis (4-phenylphenyl) carbonate And the like. In addition, it goes without saying that dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like can be used as desired. Of these, diphenyl carbonate is mentioned as a preferable one in terms of reactivity, stability against coloring of the obtained resin, and further from the viewpoint of cost.

The catalyst system has already been described,
A catalyst system containing (a) a basic nitrogen compound or a basic phosphorus compound and (b) an alkali metal compound is used. The amount of the alkali metal used is 0.01 to 5 per mole of the aromatic dihydroxy compound. It is preferable to keep the micro equivalent. By using the amount of the alkali metal element derived from the catalyst system in the polycarbonate resin in such an amount range, the production of the polycarbonate can be efficiently performed with good productivity, and the physical properties of the obtained polycarbonate also achieve the objects of the present invention. Therefore, it is preferable.

The alkali metal compound used in the present invention as a catalyst includes, for example, an alkali metal hydroxide,
Hydrocarbon compounds, carbonates, acetates, nitrates, nitrites,
Examples include sulfites, cyanates, thiocyanates, stearates, borohydrides, benzoates, borohydrides, bisphenol salts, and phenol salts.

Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, and acetic acid. Lithium, sodium nitrate,
Potassium nitrate, rubidium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, rubidium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate,
Lithium cyanate, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, cesium thiocyanate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride , Sodium phenylated, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, monosodium salt , Monopotassium salt, sodium potassium salt, sodium lithium salt,
And phenol sodium salts, potassium salts and lithium salts.

The alkali metal compound used as a catalyst is used in an amount of 0.01 to 5 microequivalents as an alkali metal element per mole of the aromatic dihydroxy compound. In the above sense, it is more preferably used in the range of 0.05 to 5 microequivalents. More preferably 0.0
Used in the range of 8-4 microequivalents. If the ratio is out of the above range, various properties of the obtained polycarbonate are adversely affected, and a transesterification reaction does not sufficiently proceed to obtain a high molecular weight polycarbonate, which is not preferable.

As the nitrogen-containing basic compound as a catalyst, for example, tetramethylammonium hydroxide (M
e ₄ NOH), tetraethylammonium hydroxide (Et4NOH), tetrabutylammonium hydroxide (Bu4NOH), benzyltrimethylammonium hydroxide (phi chromatography CH2 (Me) 3NOH), and hexadecyl trimethyl ammonium alkyl such hydroxides, aryl, Alkyl such as ammonium hydroxides having an alkylaryl group, tetramethylammonium acetate, tetraethylammonium propionate, tetrabutylammonium lactate, benzyltrimethylammonium acetate, hexadecyltrimethylammonium benzoate, and tetramethylammonium carbonate Ammonium carboxylates having an aryl, alkylaryl group, etc., and ammonium Non-carbonated salts, triethylamine,
Tertiary amines such as tributylamine, dimethylbenzylamine, hexadecyldimethylamine, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tet
Labutylammonium borohydride (Bu ₄ NB
H ₄ ), basic salts such as tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), and tetramethylammonium traphenyl borate (Me ₄ NBPh ₄ ).

Examples of the basic phosphorus compound include alkyl, aryl and alkylaryl groups such as tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, benzyltrimethylphosphonium hydroxide and hexadecyltrimethylphosphonium hydroxide. Alkyl, aryl, alkylaryl groups such as phosphonium hydroxides, tetramethylphosphonium acetate, tetraethylphosphonium propionate, tetrabutylphosphonium lactate, benzyltrimethylphosphonium acetate, hexadecylphosphonium benzoate, and tetramethylphosphonium carbonate Phosphonium carboxylate, and phosphonium carbonates having Rui can include tetramethyl phosphonium borohydride, tetrabutyl phosphonium borohydride, tetrabutyl phosphonium tetraphenyl borate, and basic salts such as tetramethyl phosphonium tiger tetraphenylborate and the like.

The basic nitrogen compound and the basic phosphorus compound are those in which the basic nitrogen compound and the basic nitrogen and phosphorus atoms in the basic phosphorus compound are 10 to 500 microequivalents per mole of the aromatic dihydroxy compound. It is preferable to use them. A more preferred use ratio is 20 for the same standard
It is a ratio that becomes ~ 500 microequivalents. A particularly preferred ratio is a ratio that results in 50 to 300 microequivalents with respect to the same standard.

In the method of the present invention, a specific salicylic acid ester is allowed to act after reaching a predetermined degree of polymerization during the melt polycondensation of the polycarbonate.
The H terminal group can be suitably reduced.

That is, the OH terminal group concentration of the polycarbonate having reached a predetermined degree of polymerization was measured by an NMR spectrometer,
The above salicylate is added in an amount of 0.7 to 1 mol of H terminal group.
The OH group concentration in the polycarbonate is adjusted to 30 eq / to by reacting 10 to 10 mol, particularly preferably 1 to 2 mol.
n or less, particularly preferably 20 eq / ton or less. Thereby, the coloring when the polycarbonate is kept at a high temperature in the air can be preferably reduced.

Specific examples of the salicylic acid ester include 2-methoxycarbonylphenyl-phenyl carbonate, 2-methoxycarbonylphenyl-2'-methylphenylcarbonate, 2-methoxycarbonylphenyl-4'-ethylphenylcarbonate, Methoxycarbonylphenyl-3′-butylphenylcarbonate, 2-methoxycarbonylphenyl-4′-dodecylphenylcarbonate, 2-methoxycarbonylphenyl-4′-hexadecylphenylcarbonate,
-Methoxycarbonylphenyl-2 ', 4'dibutylphenylcarbonate, 2-methoxycarbonylphenyldinonylphenylcarbonate, 2-methoxycarbonylphenyl-cyclohexylphenylcarbonate,
2-methoxycarbonylphenyl-biphenyl carbonate, 2-methoxycarbonylphenyl-cumylphenyl carbonate, 2-methoxycarbonylphenyl-
2'-methoxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-butoxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-cumyloxyphenyl carbonate, di (2-methoxycarbonylphenyl) carbonate, 2-methoxycarbonylphenyl -2-ethoxyphenyl carbonate, and 2
2-methoxycarbonylphenyl aryl carbonates such as -methoxycarbonylphenyl-2 '-(O-methoxycarbonylphenyl) oxycumylphenyl carbonate; 2-methoxycarbonylphenyl-methyl carbonate, 2-methoxycarbonylphenyl-butyl carbonate, -Methoxycarbonylphenyl-
Cetyl carbonate, 2-methoxycarbonylphenyl-lauryl carbonate, 2-methoxycarbonylphenyl-2′-ethoxycarbonylethyl carbonate,
And 2-methoxycarbonylphenyl-2 ′-(O-
2-methoxycarbonylphenyl-alkyl carbonates such as methoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-ethoxycarbonylphenyl-phenylcarbonate, 2-ethoxycarbonylphenyl-propylphenylcarbonate, 2-ethoxycarbonylphenyl-hexylphenylcarbonate, -Ethoxycarbonylphenyl-dibutylphenyl carbonate, 2-ethoxycarbonylphenyl-dinonylphenyl carbonate, 2-ethoxycarbonylphenyl-cyclohexylphenyl carbonate, 2-
Ethoxycarbonylphenyl-cumylphenyl carbonate, 2-ethoxycarbonylphenyl-4′-ethoxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl-4′-cumyloxyphenyl carbonate, 2-ethoxycarbonylphenyl-carbonate, and di (2 2-ethoxycarbonylphenyl-aryl carbonates such as -ethoxycarbonylphenyl) carbonate; 2-ethoxycarbonylphenyl-methyl carbonate, 2-ethoxycarbonylphenyl-octyl carbonate, 2-ethoxycarbonylphenyl-2'-methoxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl-carbonate,
And 2-ethoxycarbonylphenyl-alkyl carbonates such as 2-ethoxycarbonylphenyl-2- (O-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; (2-methoxycarbonylphenyl) benzoate, (2-methoxycarbonylphenyl) -4 -Methylbenzoate, (2-methoxycarbonylphenyl) -4-butylbenzoate, (2-methoxycarbonylphenyl) -4-cumylbenzoate, (2-methoxycarbonylphenyl) -4-butoxybenzoate, (2-methoxycarbonylphenyl) )
-2-methoxycarbonylbenzoate, (2-methoxycarbonylphenyl) -4-methoxycarbonylbenzoate, (2-methoxycarbonylphenyl) -4-
Ethoxycarbonylbenzoate, 3- (O-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2 ′
-Methoxycarbonylphenyl) ester, and 4-
(O-ethoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, (2'-methoxycarbonylphenyl) ester of aromatic carboxylic acid; (2-ethoxycarbonylphenyl) benzoate, (2- (Ethoxycarbonylphenyl) -4-methylbenzoate, (2-ethoxycarbonylphenyl) -4-butylbenzoate, (2-
(Ethoxycarbonylphenyl) -4-nonylbenzoate, (2-ethoxycarbonylphenyl) -4-cumylbenzoate, (2-ethoxycarbonylphenyl)-
4-methoxybenzoate, (2-ethoxycarbonylphenyl) -4-nonyloxybenzoate, (2-ethoxycarbonylphenyl) -4-cumyloxybenzoate, and (2-ethoxycarbonylphenyl)-
(2'-ethoxycarbonylphenyl) ester of aromatic carboxylic acid such as 4-ethoxycarbonylbenzoate; (2-methoxycarbonylphenyl) acetate, (2-methoxycarbonylphenyl) stearate, (2-methoxycarbonylphenyl) oleate,
Aliphatic carboxylic esters such as (2-ethoxycarbonylphenyl) cyclohexanecarboxylic acid ester, bis (2-methoxycarbonylphenyl) succinate, and bis (2-methoxycarbonylphenyl) adipate.

In the present invention, it is preferable to reduce the residual melting activity of the polycarbonate to 0.5% or less at or after the completion of the melt polycondensation. By such treatment, the stability of the polycarbonate resin under hydrolysis conditions can be preferably improved. In order to achieve this object, one or more of a sulfonate, a phosphonium sulfonate, or an ammonium salt is used in an amount of from 0.5 to 0.5 per chemical equivalent of an alkali metal element of an alkali metal compound used as a transesterification catalyst. 3
It can be achieved by applying 0 chemical equivalents, more preferably 0.9 to 10 chemical equivalents.

The phosphonium sulfonate or ammonium salt used in the present invention is

[0032]

A ¹ -(-SO ₃ X ¹ ) _m (I) (where A ¹ is an m-valent hydrocarbon group which may have a substituent, X ¹ is ammonium, Or m is an integer of 1 to 4. Here, as the ammonium cation and the phosphonium cation,

[0033]

+ N (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) (Ia) + P (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) (Ib) (Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group).

[0034]

Embedded image _{^{+ X 2 -A 2 -SO 3 -}} ··· (II) (. Wherein A ² is a divalent hydrocarbon group, ⁺ X ² is an ammonium or phosphonium cation,) where Ammonium or phosphonium cations

[0035]

-N ⁺ (R ⁵ ) (R ⁶ ) (R ⁷ ) (IIa) -P ⁺ (R ⁵ ) (R ⁶ ) (R ⁷ ) (IIb) (where R ^{5 to} R ⁷ are each independently a hydrogen atom or a monovalent hydrocarbon group.).

[0036]

Embedded image A ³ -( ⁺ X ³ ) n · (R—SO ₃ ⁻ ) n (III) (where A ³ is an n-valent hydrocarbon group, and X ³ is ammonium or phosphonium A cation, where n is 2 to 4
Is an integer. Here, examples of the ammonium or phosphonium cation include those represented by (IIa) or (IIb). )

Specific examples of the compound represented by the above formula (I) include, for example: tetrabutylphosphonium octylsulfonate, tetraphosphonium decylsulfonate, tetramethylphosphonium benzenesulfonate, tetrabutylbenzenesulfonate Phosphonium salts,
Tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetramethylammonium decylsulfonate, tetraethylammonium benzenesulfonate, tetrabutylammonium dodecylbenzenesulfonate ^{_{, - SO 3 - (CH 2}} ) 3 -P + (C 2 H 5) 3, - S
_{O 3 - (CH 2) 15} -P + (C 4 H 9) 3, - SO 3 - (C
H ₂ ) ₁₅ −N ⁺ (C ₄ H ₉ ) ₃ , ｛(C ₄ H ₉ ) ₃ P ⁺ −
(CH ₂ ) ₁₀ -P ⁺ (C ₄ H ₉ ) ₃ }, and (CH ₃ -C ₆
H ₄ —SO ₃ ⁻ ) _{2 and} so on.

The sulfonic acid ester usable in the present invention includes, for example, methyl decane sulfonate, butyl decane sulfonate, pentyl nonane sulfonate, ethyl dodecyl sulfonate, nonyl hexadecyl sulfonate, methyl benzene sulfonate, toluene sulfonic acid Butyl, t
-Octyl butylbenzenesulfonate, 2,4-di-t-
Examples thereof include propyl butylbenzenesulfonate, butyl dodecylbenzenesulfonate, ethyl hexadecylbenzenesulfonate, nonyl naphthalenesulfonate, and pentyl diphenylsulfonate.

In the present invention, in order to produce a stabilized polycarbonate composition, it is preferable to add 0.001 to 10 parts by weight of a resin property improving agent per 100 parts by weight of the polycarbonate resin. As the resin property improver used in the present invention, for example, phosphorus-based antioxidants, phenol-based antioxidants, and higher fatty acid esters are the first target, but other commonly used resin property improvers It does not limit the use of.

What is important to achieve the object of the invention is that
The purpose is to keep the content of acidic substances in these resin property improvers to a low level. That is, the acid value of these agents is 10e
It is necessary to keep q / ton or less to achieve the object of the present invention. The acid value of such an agent is 10 eq / ton
To achieve the following, a suitable low-boiling organic solvent, in particular, having a boiling point of 15
0 ° C. or lower, more preferably 100 ° C. or lower, room temperature or higher,
More preferably, it can be easily achieved by dissolving in an inert solvent at 30 ° C. or higher, for example, acetone, tetrahydrofuran, methyl ethyl ketone, etc., treating with an ion exchange resin and removing the solvent under reduced pressure.

Examples of the phosphorus acid value inhibitor used in the present invention include: bis (2,3-di-t-butylphenyl) pentaerythrityl diphosphite and bis (2,6-di-
t-butyl-4-methylphenyl) pentaerythrityl diphosphite, bis (nonylphenyl) pentaerythrityl diphosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, phenyl diisooctyl phosphite, 2-ethylhexyl diphenyl Phosphite, tetraphenylpropylene glycol diphosphite, tetra (tridecyl) -4,4'-
Isopropylidene diphenyl diphosphite, 2,2-
Methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and 2- {2,4,8,10-
Tetrakis (1,1-dimethylethyl) dibenzo ｛d,
f {1,3,2} dioxaphosphepin 6-yl}
Oxy} -N, N-bis {2-} 2,4,8,10-
Tetrakis (1,1 dimethylethyl) dibenzo ｛d,
f {1,3,2} dioxaphosphepin 6-yl}
Arylalkyl phosphites such as oxy {-ethyl} ethanamine, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trimeoctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, distearyl pentaery Stildiphosphite, bis (tridecyl) pentaerythrityldiphosphite, tris (2-
Chloroethyl) phosphite, and tris (2,3-
Trialkyl phosphites such as dichloropropyl) phosphite, and tricycloalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4 Triarylphosphites such as di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite and tris (hydroxyphenyl) phosphite, pentaerythrityl phosphite polymer of hydrogenated bisphenol-A, triethyl phosphate, Tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate And trialkyl phosphates such as tris (2,3-dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphite; and triphenyl phosphate, tricresyl phosphate, tris (ethylphenyl) phosphate, tris (2,4-di-tert-butylphenyl) phosphate and triarylphosphates such as tris (nonylphenyl) phosphate and tris (hydroxyphenyl) phosphate; tetrakis (2,4-di-tert-butylphenyl) -4,4 -Phosphites such as -biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) 4,4'-phenylenediphosphinate. These may be used alone or as a mixture of two or more.

Examples of the phenolic acid value inhibitor include n-octadecyl-3- (4′-hydroxy-3 ′,
5′-di-t-butylphenyl) propionate, tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate} methane,
1,1,3-tris (2-methyl-4-hydroxy-5
-T-butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butylbenzyl) malonate, triethylene glycol-bis {3- (3-t-
(Butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate}, 2,4-bis- (n-octylthio) -6- (4-hydroxyphenyl-3,5-di-t
-Butyl-anilino) -1,3,5-triazine, pentaerythrityl-tetrakis {3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate
2,2-thiodiethylenebis {3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate
2,2-thiobis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5-di-
t-butyl-4-hydroxy-hydrocinnamamide),
3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene, bis (3,5-di-
Ethyl t-butyl-4-hydroxybenzylsulfonate) calcium, tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) -isocyanurate, 2,4-
Bis {(octylthio) methyl} -O-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2 (4 ′, 8 ′ , 12'-Trimethyltridecyl) chroman-6-ol, N, N'-bis {3-
(3,5-di-t-butyl-4-hydroxyphenyl)
And propionyl dihydrazine and 4-hydroxymethyl-2,6-di-t-butylphenol. These may be used alone or as a mixture of two or more.

As the release agent used in the present invention, conventionally known release agents can be favorably used. For example, an ester of an aliphatic carboxylic acid and an alcohol can be preferably used. Saturated or unsaturated monohydric alcohols such as, for example, saturated or unsaturated aliphatic mono-, di- or tricarboxylic acids and ethanol, butanol, or stearyl alcohol;
Saturated or unsaturated dihydric alcohols such as ethylene glycol, 1,4-butenediol or diethylene glycol, or saturated or unsaturated trihydric alcohols such as glycerol, pentaerythritol or the like; Examples thereof include, but are not limited to, esters with a polyhydric alcohol or a saturated or unsaturated polyhydric alcohol such as pentavalent or more.

Here, the aliphatic carboxylic acid includes an alicyclic carboxylic acid. Preferably an expression

[0045]

Embedded image C _n H _2n + 1 -COOH or formula HOOC-C _n H _2n
A fatty acid represented by —COOH (where n is an integer of 5 to 34);

[0046]

_{Embedded image} C _{n ′} H _{2n ′ + 1} —CH ₂ OH, (R ¹ ) (R ² ) C
_{(CH 2 OH) 2, (} HOCH 2) 4 -C, (R 3) (CH 2
OH) ₂ C—R ⁴ , C (CH ₂ OH) ₂ (R ⁵ ), (HOC
^{_{H 2) 3 -C-R 4}} -C- (CH 2 OH) 3, and HOC
H ₂ —CH ₂ —CH (CH ₃ ) —CH ₂ —CH ₂ OH (where n is an integer of 1 to 20, and R ¹ and R ² each independently have a substituent having 1 to 10 carbon atoms) An optionally substituted alkyl group or R ¹ and R ² combine to form a 5- or 6-membered ring;
³ and R ⁵ are each independently an alkyl group which may have a substituent having 1 to ⁴ carbon atoms, and R ⁴ is an alkylene group having 1 to ⁴ carbon atoms or — (CH ₂ ) _{n ″} —O— ( CH ₂₎ n _"- (where n" uses an ester of an alcohol represented by any of integer from 1 to 4)).

Specific examples of the carboxylic acid represented by the above formula include: stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachiic acid, behenic acid, lignoceric acid serotinic acid, mericinic acid, tetratriacontanic acid,
Glutaric acid, adipic acid, azelaic acid and the like can be mentioned. Specific examples of the alcohol represented by the above formula include glycerin, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, pentaerythritol, ditrimethylolpropane, and dipentaerythritol.

The ester compound of a carboxylic acid and an alcohol which can be used as a releasing agent includes, specifically, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol monolaurate,
Glycerol tribehenate, glycerol dilaurate, glycerol monostearate, trimethylolpropane tristearate, trimethylolpropanediolate, trimethylolpropane monostearate, paraffin wax, polysiloxane, polycaprolactone, erucamide, and the like.

In order to achieve the desired object of the present invention, various conventionally known additives can be used. For example, as a light stabilizer,
2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,
5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5
-T-octylphenyl) benzotriazole, 2-
Benzotriazoles such as (3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole and 2- {2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) phenyl} benzotriazole Compounds, benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,4-
Benzoate compounds such as di-t-butylphenyl and 3,5-di-t-butyl-4-hydroxybenboate are exemplified.

UV absorbers such as ethyl-2-cyano-
Cyanoacrylate compounds such as 3,3-diphenylacrylate, and quencher such as nickel dibutyldithiocarbamate and nickel such as {2,2′-thiobis (4-t-octylphenolate)}-2-ethylhexylamine nickel Examples of the system quencher and metal deactivator include N, N '-{3- (3,5-
Compounds such as di-t-butyl-4-hydroxyphenyl) propionyl dihydrazine, metal soaps such as calcium stearate and nickel stearate, and nucleating agents such as di (4-t-butylphenyl) phosphonic acid Examples include sodium, dibenzylidene sorbitol, and sorivitol-based and phosphate-based compounds such as sodium salt of methylenebis (2,4-di-t-butylphenol acid phosphate).

Examples of the antistatic agent include quaternary ammonium salts such as (β-lauramidopropyl) trimethylammonium sulfate and alkyl phosphate compounds. Examples of the flame retardant include halogen-containing phosphates such as tris (2-chloroethyl) phosphate, halides such as hexabromocyclododecane and decabromophenyl oxide, antimony trioxide, antimony pentoxide, and aluminum hydroxide. Metal-inorganic compounds and mixtures thereof are mentioned.

[0052]

According to the present invention, 2,2-form having a specific crystal structure is provided.
By using bis (4-hydroxyphenyl) propane, an aromatic polycarbonate having a good color tone can be produced.

[0053]

EXAMPLES In the following examples, orthorhombic 2,2
When 2-bis (4-hydroxyphenyl) propane is used, it shows that a polycarbonate having a good color tone is obtained, and in particular, when superiority of the color tone is obtained when used in combination with various additives. In the examples, orthorhombic 2,2-bis (4-hydroxyphenyl) propane is
In the comparative example, monoclinic 2,2-bis (4-hydroxyphenyl) propane was used.

[Examples 1 to 8, Comparative Examples 1 to 8] 2,2-
Bis (4-hydroxyphenyl) propane; (crystal system:
228 parts by weight, diphenyl carbonate; 2
20 parts by weight of the catalyst and the kind and amount of the catalyst shown in the table were charged into a reactor equipped with a stirrer, a distillation column and a decompression device, and after displacing with nitrogen, they were dissolved at 140 ° C. After stirring for 30 minutes,
The internal temperature was raised to 180 ° C., the reaction was performed at an internal pressure of 100 mmHg for 30 minutes, and the phenol produced was distilled off.

Then, the internal temperature was raised to 200 ° C., the pressure was gradually reduced, and the reaction was carried out while distilling off phenol at 50 mmHg for 30 minutes. Furthermore, the temperature was gradually raised and reduced to 220 ° C. and 30 mmHg, and the reaction was carried out at the same temperature and pressure for 30 minutes, and further 240 ° C., 10 mmHg, 260 ° C. and 1 mm
Hg, 270 ° C., 1 mmHg or less, the temperature was repeatedly increased and reduced in the same procedure as above, and the reaction was continued.

Finally, the polymerization reaction was continued at the same temperature and the same pressure, and judging from the stirring power of the polymerization reactor, when the intrinsic viscosity of the polycarbonate became about 0.35 (or about 0.45), the polymer was obtained. Was collected and the intrinsic viscosity and terminal hydroxyl group concentration were measured. The intrinsic viscosities and terminal hydroxyl group concentrations of the obtained polymers are shown in Tables 1 and 2 below. Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1 are polycarbonate compositions for general molding, and Examples 5 to 8 and Comparative Examples 5 to 8 in Table 2 are polycarbonate compositions for disk molding.

[Terminal Capping Reaction, Catalyst Inactivation] A predetermined amount of a terminal capping agent (2-methoxycarbonylphenyl-phenyl-carbonate) per 100 parts by weight of the polycarbonate was added at 270 ° C. under a reduced pressure of 50 mmHg. Thereafter, the terminal blocking reaction was continued at 270 ° C. and 1 mmHg or less for 5 minutes. Thereafter, a catalyst deactivator shown in Tables 1 and 2 below was added, and mixed and stirred at the same temperature and pressure for 10 minutes to deactivate and deactivate the catalyst. By converting the OH group of the polycarbonate to a phenoxy group or another inert group,
It is suitable for keeping the coloring of the resin at a low level when used under heating conditions in an oxidizing atmosphere such as air. Tables 1 and 2 below show the terminal hydroxyl group concentration, intrinsic viscosity, and hue (color L / a / b value) of the obtained polycarbonate.
In the case where there is a separate description in the table, the resin property improver described in the following Tables 1 and 2 was added to the resin property improver described in the table per 100 parts by weight of the polymer, and extruded with a biaxial ruder to form chips.

[Analysis: Measurement of Physical Properties of Polycarbonate Composition and Raw Materials] 1) Intrinsic viscosity [η] of polycarbonate was measured in methylene chloride at 20 ° C. using an Ubbelohde viscosity tube.

(2) Hue; (a) Chip hue: The chip hue was determined by Nippon Denshoku Co., Ltd.
The chip color L / a / b value was measured with a 1001DP color difference meter. (B) Molded product hue: A 50 mm x 50 mm x 5 mm flat plate was molded with a Neomat N150 / 75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a cylinder temperature of 280 ° C and a molding cycle of 3.5.
Molded in seconds, and the b value of the flat plate was measured by Z-100 manufactured by Nippon Denshoku
It was measured with a 1DP colorimeter. The larger the b value, the worse the hue.

3) Transparency: The total light transmittance of the flat plate was measured by NDH- # 80 manufactured by Nippon Denshoku Co., Ltd. The higher the total light transmittance, the better the transparency.

4) Terminal hydroxyl group concentration: 0.02 g of sample
Was dissolved in 0.4 ml of chloroform, and 1H-
The terminal hydroxyl group and the terminal phenyl group were measured using NMR (EX-270 manufactured by JEOL Ltd.), and the terminal hydroxyl group concentration was measured.

5) Melt viscosity stability: Using a rheometrics RAA type flow analyzer under a nitrogen stream, shear rate 1
rad / sec. The absolute value of the change in melt viscosity measured at 300 ° C. was measured for 30 minutes, and the rate of change per minute was determined. For good long-term stability of the polycarbonate resin composition, this value should not exceed 1%.

[0063]

[Table 1]

[0064]

[Table 2]

Note 1) DBSP Tetrabutylphosphonium dodecylbenzenesulfonate; sodium dodecylbenzenesulfonate is reacted with a commercially available equimolar tetrabutylphosphonium bromide in water / acetone {volume (50/50)}, using methylene chloride. Extracted. The methylene chloride solution was washed with water and distilled off under vacuum to obtain tetrabutylphosphonium dodecylbenzenesulfonate, which was then treated with an ion exchange resin and activated carbon in an acetone solvent.

Note 2) TDBPP; Tris (2,4-di-tert-butylphenyl) phosphate;
PNPP was subjected to an ion exchange resin treatment and further to an activated carbon treatment in an acetone solvent.

Note 3) ODP; octadecyl-3- (3,
5-Di-t-butyl-4-hydroxyphenyl) propionate; commercial product * Note 3 is not shown in the table for the treated product (Note 4 below) in both Examples and Comparative Examples.

Note 4) The above ODP was dissolved in acetone and activated carbon treatment was added.

Note 5) PTS: pentaerythritol tetrastearate: Reaction synthesis was performed from pentaerythritol and stearic acid chloride in tetrahydrofuran using tetraethylamine as an acid acceptor. After the obtained tetrafuran solution was treated with activated carbon, tetrahydrofuran was distilled off under reduced pressure.

Note 6) GMS; glycerin monostearate; a commercially available product was dissolved in acetone, treated with activated carbon, and acetone was removed under reduced pressure.

Note 7) PTSB; P-butyltoluenesulfonate, a commercially available product was dissolved in acetone, activated carbon was added at 2 wt%, and after a treatment all day long, the activated carbon was filtered and acetone was removed under reduced pressure.

Note 8) TMAH; tetramethylammonium hydroxide

Note 9) TBPH: tetrabutylphosphonium hydroxide

Note 10) SAMDPC: Phenyl chloroformate and methyl salicylate were reacted in methylene chloride with a small excess of triethylamine as an acid absorbent. The obtained methylene chloride solution was washed with water, further neutralized with a dilute aqueous hydrochloric acid solution, and then repeatedly washed three to five times. Obtained
After the methylene chloride solution was treated with an ion exchange resin and activated carbon, the solvent was distilled off in vacuo, and the obtained crystals were recrystallized from xylene.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Katsuji Sasaki 2-1 Hinodecho, Iwakuni-shi, Yamaguchi Prefecture F-term in Iwakuni Research Center, Teijin Limited 4J029 AA09 AB04 AC01 AC02 AD10 BA02 BA03 BA05 BA07 BB04A BB05A BB06A BB09A BB12A BB13A BB13B BD04A BF09 BF14A BF25 BG05X BG07X BG08X BG24X BH02 CA04 CA06 CB05A CB06A CC06A CD03 DB07 DB10 DB13 EA02 EB05A EC06A HC02 HC04A HC05A JA091J03 J01 J01J01 J01 J01J01 J01 J01J01 J01 JA201 JA1J01

Claims (2)

[Claims] 1. A melt polycondensation of a dihydroxy compound having 2,2-bis (4-hydroxyphenyl) propane as a main component and an aromatic carbonate having diphenyl carbonate as a main component in the presence of a basic transesterification catalyst. In producing the sensitized aromatic polycarbonate, the 2,2-bis (4-hydroxyphenyl) propane is
A method for producing an aromatic polycarbonate, characterized by having an orthorhombic crystal structure. 2. The basic transesterification catalyst is a catalyst containing (A) a basic nitrogen compound or a basic phosphorus compound and (A) an alkali metal compound, and (A) a basic nitrogen compound or a basic phosphorus compound. Of 10 per mole of 2,2-bis (4-hydroxyphenyl) propane
Claims 1 to 500 micromoles, and (a) 0.01 to 5 microequivalents per mole of 2,2-bis (4-hydroxyphenyl) propane, using an alkali metal compound as an alkali metal element. 2. The method for producing an aromatic polycarbonate according to 1.