JP3187272B2 - Manufacturing method of aromatic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aromatic polycarbonate. More specifically, there is almost no coloring,
The present invention relates to a method for producing a polycarbonate, which has a small decrease in the degree of polymerization at the time of molding and has little branching or insoluble matter.

[0002]

2. Description of the Related Art Polycarbonate is widely used because it has excellent mechanical properties such as impact resistance, and also has excellent heat resistance and transparency. As a method for producing such a polycarbonate, a method of directly reacting an aromatic dihydroxy compound such as bisphenol with phosgene (interface method), or a method in which an aromatic dihydroxy compound such as bisphenol and a diaryl carbonate such as diphenyl carbonate are melted. A method of transesterification (melting method) and the like are known.

Among such production methods, a method for producing a polycarbonate by a transesterification reaction between an aromatic dihydroxy compound and a diaryl carbonate will be described. This method uses a metal organic acid salt, an inorganic acid salt, or a catalyst as a catalyst. A method in which an aromatic dihydroxy compound and a diaryl carbonate are subjected to transesterification while being melted by heating, for example, finally to 250 to 330 ° C. under reduced pressure using an oxide, a hydroxide, a hydride or an alcoholate. is there. This method has an advantage that polycarbonate can be produced at a lower cost than the above-mentioned interface method, but has a problem that the hue is not preferable because the polymer is exposed to a high temperature for a long time.

Japanese Patent Application Laid-Open No. 62-199618 discloses a method for producing a polyester carbonate by transesterifying a diaryl carbonate and an alkyl alkyl aromatic dicarboxylate in the molten state in the presence of a catalyst. The publication discloses that as a catalyst, (1) an alkali metal and a compound thereof, (2) a compound of an element of Group II (Group 2) and Group III (Group 13) of the periodic table, and (3) a compound of the above element Other compounds such as germanium, tin, lead, zinc, cadmium and the like are exemplified. The examples disclose a method for producing polyester carbonate using only a tin compound as a catalyst.

[0005] JP-A-54-63023 discloses the following formula:

[0006]

Embedded image R _3-k Sn (OR ¹ ) _{1 + k} [where R is a hydrocarbon residue, R ¹ is a hydrocarbon residue, k
Represents an integer of 0 to 2, and two R ¹ may represent one alkylene group. A transesterification reaction between a hydroxy compound and a carbonate in the presence of a tin alkoxide represented by the formula: Examples of the alkoxide include trialkylalkoxytin, dialkyldialkoxytin, diaryldialkoxytin, and alkyltrialkoxytin.

Japanese Patent Application Laid-Open No. 57-2334 discloses that a dihydric phenol and a dialkyl carboxylate are subjected to a transesterification reaction in the presence of an organotin (IV) compound (a) and a monohydric phenol (b) to produce an aromatic compound. A method for producing an aromatic polycarbonate is disclosed. The organic tin (IV) compound has the following formula

[0008]

(R ¹ ) _4-x Sn (Y) _x [where Y represents an O—CO—R ² , OH or OR ² group, and R ² represents a C ₁ -C ₁₂ alkyl group; _{5 ~C 12}
An aryl group or C ₇ -C ₁₃ aralkyl group, R ¹
Has the same meaning as R ² , and x is an integer of 1 to 3], and di (C ₁ -C ₁₂ alkyl) S
nO or the following formula

[0009]

Embedded image

[Wherein R ⁴ has the same meaning as R ² ;
R ⁵ has the same meaning as R ² or represents an OR ⁶ group. ] It is a compound represented by these. In the examples, ethyltin triisooctylate and tributoxyethyltin are used.

JP-A-6-145334 discloses the following formula:

[0012]

RnSi (OR ¹ ) _4-n wherein R and R ¹ are each independently a C ₁ -C ₂₀ hydrocarbon group, and n is 0, 1, 2 or 3. Discloses a method for producing a polycarbonate by melt-polycondensing an aromatic diol compound and a carbonic acid diester in the presence of an organosilicon compound.

Examples of the transesterification catalyst used in the melt polycondensation include acetates, carbonates, borates, nitrates, oxides, hydroxides of metals such as alkali metals, alkali metals, tin, nickel and titanium. , Hydrides and alcoholates are disclosed. In the examples, dibutyltin oxide (Examples 1 to 8) and dibutyltin laurate (Example 9) are used.

JP-A-5-202180 discloses a linear polycarbonate having a branch parameter G of 0.8 to 1.0. The branching parameter G is the intrinsic viscosity [η] at 20 ° C. in methylene chloride, and the intrinsic viscosity [η] at 20 ° C. of methylene chloride of a linear polycarbonate having the same weight average molecular weight measured by a light scattering method.
_Since it is defined as a value divided by _lin , it can be said that the smaller the value G, the greater the degree of branching.

According to the publication, an alkali metal compound or an alkaline earth metal compound known as a transesterification catalyst is highly active as a catalyst, but forms a branched structure by a side reaction or partially reacts with a methylene chloride solvent. It describes that there are disadvantages such as insolubility or excessive coloring.

[0016] Therefore, in the publication, as a catalyst, an element of Group IIb (Group 12) such as zinc and cadmium, and a periodic table IVb such as silicon, germanium, tin and lead are used.
It is disclosed that a compound containing an element of Group V (Group 14) and an element of Group Vb of Periodic Table (Group 15) such as antimony and bismuth is used. Specifically, silicon oxide, germanium oxide, germanium hydroxide, second oxide
Tin and the like are exemplified.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for producing an aromatic polycarbonate by a melt polymerization method. It is another object of the present invention to provide a method for producing an aromatic polycarbonate having no coloring and having few branches and insolubilized substances by a melt polycondensation method. Still another object of the present invention is to provide an aromatic polycarbonate in which a side reaction such as a branching reaction during molding processing is suppressed, and molding is performed in a processing apparatus, and coloring, insolubilization, generation of foreign matter, or reduction in molecular weight is suppressed. It is to provide a manufacturing method. Still another object of the present invention is to provide a method for producing the aromatic polycarbonate as described above at a high polymerization rate with high productivity. Still another object of the present invention is to provide a catalyst or a catalyst composition for producing the aromatic polycarbonate as described above. Still other objects and advantages of the present invention will become apparent from the following description.

[0018]

According to the present invention, the above-mentioned object and advantages of the present invention are to provide an aromatic dihydroxy compound and a diaryl carbonate, wherein (a) an ate complex of a metal element of Group 14 of the Periodic Table. An alkali metal salt and (b)
At least one alkali metal salt selected from the group consisting of alkali metal oxoacids of the same metal element, wherein the metal element of Group 14 of the periodic table is silicon, germanium,
This is achieved by a method for producing an aromatic polycarbonate, characterized in that polycondensation is performed using a compound selected from the group consisting of tin and lead as a polycondensation catalyst.

The present invention is a method for producing an aromatic polycarbonate by polycondensing an aromatic dihydroxy compound and a diaryl carbonate as described above.

As the aromatic dihydroxy compound, for example, the following formula (I)

[0021]

Embedded image

R ¹ and R ² are the same or different and are each a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms,
And R ³ and R ⁴ are the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁵ is a hydrocarbon group having 4 to 20 carbon atoms. Wherein m and n are the same or different and are 0 or an integer of 1 to 4. ] Are preferably used.

In the formula (I), R ¹ and R ² are the same or different and are a halogen atom, a hydrocarbon having 1 to 12 carbons or a hydrocarbon —O or —S group having 1 to 12 carbons. Preferred examples of the halogen atom include chlorine and fluorine. Further, as the hydrocarbon group having 1 to 12 carbon atoms, for example, 1 to 12 carbon atoms
Twelve aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 6 to 12 carbon atoms are preferred. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include an alkyl group having 1 to 12 carbon atoms and an alkenyl group having 2 to 12 carbon atoms. Such an alkyl group or alkenyl group may be linear or branched. Examples of alkyl groups include, for example, methyl, ethyl,
n-propyl, iso-propyl, n-butyl, sec
-Butyl, tert-butyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl. Examples of the alkenyl group include, for example, ethenyl, propenyl, butenyl, pentenyl, decene-1-
Yl and cyclohexen-1-yl.

Further, examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl, tolyl, ethylphenyl, naphthyl, methylnaphthyl and biphenyl.

As the C 1-12 hydrocarbon —O or —S group, an oxygen atom (O) or a sulfur atom (S) is added to the above specific examples of the C 1-12 hydrocarbon group. And groups corresponding to the groups. For example, methoxy,
Ethoxy, hexyloxy, octyloxy, phenoxy, methylphenoxy and naphthyloxy, methylthio, ethylthio, phenylthio groups are preferred.

M and n are the same or different and are 0 or an integer of 1 to 4. When m is 0, it means that there is no substituent R ¹ , and when n is 0, it means that there is no substituent R ² .

[0027]

Embedded image

Here, R ³ and R ⁴ may be the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms. As the halogen atom and the hydrocarbon group having 1 to 12 carbon atoms, the same groups as those exemplified for R ¹ and R ² can be exemplified.

R ⁵ is a hydrocarbon group having 4 to 20 carbon atoms. As such a hydrocarbon group, a divalent aliphatic hydrocarbon group such as an alkylene group, an alkenylene group, and a fluorene group can be preferably mentioned. Such an alkylene group or alkenylene group may be linear or branched. Examples of the alkylene group include tetramethylene, 1- or 2-methylpropylene, and pentamethylene. Examples of the alkenyl group include butenylene and pentenylene.

Examples of the compound represented by the formula (I) include bis (4-hydroxyphenyl) methane and 1,1-
Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy Bis (hydroxyaryl) cycloalkanes such as phenyl) cyclohexane and 9,9-bis (4-hydroxyphenyl) fluorene; dihydroxyaryl ketones such as 4,4'-dihydrodiphenyl ketone; 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxy-
Dihydroxyaryl ethers such as 3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-
Dihydroxydiaryl sulfides such as dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulphoxide, 4,4'-dihydroxy-3,3'-
Dihydroxydiarylsulfoxides such as dimethyldiphenylsulfoxide; 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-
Dihydroxydiarylsulfones such as dimethyldiphenylsulfone; and 4,4'-dihydroxybiphenyls such as 4,4'-dihydroxybiphenyl.

Of these, in particular, 2,2-bis (4-
(Hydroxyphenyl) propane (bisphenol A) is preferably used. These aromatic dihydroxy compounds can be used alone or in combination.

As the other raw material to be polycondensed with the aromatic dihydroxy compound as described above, di (substituted or unsubstituted aryl having 6 to 20 carbon atoms) carbonate is preferably used. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, and a halogen atom.

The diaryl carbonate includes
For example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (m-
(Cresyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bis (2-methoxyphenyl) carbonate, and the like. Of these, diphenyl carbonate is particularly preferably used. These diaryl carbonates can be used alone or in combination. The diaryl carbonate as described above is used in an amount of usually 1.0 to 1.30 mol, preferably 1.0 to 1 mol of the aromatic dihydroxy compound.
Desirably, it is used in an amount of 1 to 1.20 mol.

The polycondensation catalyst used in the present invention includes (a) an alkali metal salt of an ate complex of a metal element belonging to Group 14 of the periodic table or (b) an oxo acid of a metal element belonging to Group 14 of the Periodic Table. It is an alkali metal salt. However, the 14th metal element of the periodic table is any of silicon, germanium, tin and lead, and carbon is not included.

(A) As an alkali metal salt of an ate complex of a metal element belonging to Group 14 of the periodic table, for example, the following formula (II)

[0036]

Embedded image M ¹ M ² X ¹ _p (OR ⁶ ) _q (II) wherein M ¹ is an alkali metal, M ² is silicon,
Germanium, tin or lead, and X ¹ has 1 to ¹ carbon atoms.
An alkyl group having 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms or a carbon number. 6 to 20 aryl groups, p and q are 0 or an integer of 1 to 5, provided that p + q is 3
Or 5. ] Are preferably used.

In the above formula (II), M ¹ is an alkali metal salt, for example, lithium, sodium,
Potassium, rubidium and cesium. Of these, sodium is particularly preferred.

M ² is silicon, germanium, tin or lead. Of these, germanium and tin are preferred.

X ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec- Butyl, iso-butyl, tert-butyl, n-pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, eicosyl. Of these, carbon numbers 1 to
Ten alkyl groups are preferred.

Examples of the cycloalkyl group having 5 to 20 carbon atoms include cyclopentyl, cyclohexyl, methylcyclopentyl, 4-methylcyclohexyl, 3,4-dimethylcyclohexyl, and decalinyl. Among them, a cycloalkyl group having 5 to 10 carbon atoms is preferable.

The aryl group having 6 to 20 carbon atoms includes, for example, phenyl, tolyl, xylyl, naphthyl and biphenyl. Of these, phenyl is particularly preferred.

R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or
To 20 aryl groups. Specific examples and preferred examples of these groups are the same as those exemplified for X ^1. , P and q are 0 or an integer of 1 to 5, provided that p + q is 3 or 5. Therefore, when p + q is 5, p and q can be either 0 or an integer of 1 to 5, but when p + q is 3, p and q are 0.
Or any of integers from 1 to 3.

In the above formula (II), when p is 0, the following formula (II) -1

[0045]

Embedded image M ¹ M ² (OR ⁶ ) _r ... (II) -1 wherein the definitions of M ¹ , M ² and R ⁶ are the same as in formula (II), and r is 3 or 5. is there. ] The above formula (II)
Is represented by the following formula (II) -2 when q is 0:

[0046]

Embedded image M ¹ M ² X ¹ _s (II) -2 wherein the definitions of M ¹ , M ² and X ¹ are the same as in formula (II), and s is 3 or 5. ].

In the above formula (II), both p and q are 0.
If not, the following formula (II) -3

[0048]

Embedded image M ¹ M ² X ¹ _t (OR ¹ ) _u (II) -3 [where M ¹ , M ² , X ¹ and R ¹ are defined by the formula (I)
Same as I), and t and u are integers from 1 to 4. However, t + u is 3 or 5. ].

Formula (II) (Formula (II) -1, (II) -2
And (II) -3) include the following compounds.

M^TwoIn which is tin (Sn): LiS
n (OMe)_Three, LiSn (OEt)_Five, LiSn (O
Bu)_Three, LiSn (On-C_TenH_{twenty one})_Five, LiSn
(OPh)_Three, LiSn (OPh)_Five, LiSnBu_Two
OMe, LiSnBu_Two(OPr)_Three, LiSnPh
(OMe) _Two, LiSnEt_Two(OPh)_Three, NaSn
(OMe)_Three, NaSn (OMe) _Two(OEt), Na
Sn (OPr)_Three, NaSn (On-C₆H₁₃)_Three,
NaSn (OMe)_Five, NaSn (OEt)_Five, NaS
n (OBu)_Five, NaSn (On-C₁₂H_{twenty five})_Five, N
aSn (OPh)_Three, NaSnBu_Two(OMe), Na
SnPh_Two(OEt), NaSn (OPh)_Five, NaS
nBu_Two(OMe)_Three, NaSnPh_Two(OPr)_Three,
NaSnBu_Two(O-β-naphthyl) _Three, Na
SnMe_Two(O-β-naphthyl)_Three, KSn
(OMe)_Three, KSn (OBu)_Three, KSn (OPh)
_Three, KSn (OMe)_Five, KSn (OC₆H₁₃)_Five, K
Sn (OPh)_Five, CsSn (OMe)_Three, CsSn
(OBu)_Three, RbSn (OMe)_Three, RbSnBu_Two
(OMe), CsSn (OBt)_Five, CsSn (O-c
yclohexyl)_Five, RbSn (OEt)_Fiveand
RbSnBu_Two(OPh)_ThreeCan be mentioned.

Compounds wherein M ² is germanium (Ge); NaGe (OMe) ₅ , NaGe (OEt) ₅ , N
aGe (OPr) ₅ , NaGe (OBu) ₅ , NaGe
(OPh) ₅ , LiGe (OMe) ₅ , LiGe (OB
u) ₅ and LiGe (OPh) ₅ .

M^TwoIs lead (Pb); LiPb
(OMe)_Five, LiPb (OBu) _Five, LiPb (OP
h)_Five, NaPb (OMe)_Five, NaPb (OE
t)_Five, NaPb (OPr)_Five, NaPb (OB
u)_Five, NaPb (OPh)_FiveCan be mentioned.

The alkali metal salt of the above-mentioned art complex can be obtained, for example, by the following reaction formula:

[0054]

## EQU1 ## M ² X ¹ _p (OR ⁶ ) _q-1 + M ¹ OR ⁶ → M ¹ M ² X ¹ _p (OR ⁶ ) _q M ² X ¹ _p-1 (OR ⁶ ) _q + M ¹ X ¹ → It can be prepared by M ¹ M ² X ¹ _p (OR ⁶ ) _q .

In the above reaction formula, M ¹ , M ² ,
The definitions of X ¹ , R ⁶ , p and q are the same as in the above formula (II).

In the method of the present invention, the alkali metal of the ate complex is used.
The genus salt can be directly added to the polycondensation reaction system.
Of course, when the compound is prepared by the above reaction scheme, the compound M
^TwoX ¹ _p(OR⁶)_q-1For example, Sn (OPh)_FourAnd M¹
OR⁶For example, NaOPh is separately added to a polycondensation reaction system.
Adds alkali metal salt of art complex in situ
It can be done.

When preparing an alkali metal salt of an ate complex according to the above formula and the above, each starting compound is used in an approximately equimolar amount or the compound containing a metal element M ^{2 of} Group 14 of the periodic table is an alkali metal salt. It is desirable to use a slightly larger amount than the other compound containing, for example, 0.1 mol or less.

(B) As the alkali metal salt of an oxo acid of a metal element belonging to Group 14 of the periodic table, for example, silicic acid (si
alkali metal salts of licic acid, stannous acid
cid) alkali metal salts, stannic acid alkali metal salts, germanium (II) acid (germanous aci)
d) alkali metal salts, germanium (IV) acid (germani
c acid) alkali metal salt, plumbous acid
) And alkali metal salts of plumbic acid can be mentioned as preferred.

The alkali metal salt of silicic acid is, for example, an acidic or neutral alkali metal salt of monosilicic acid or a condensate thereof, such as monosodium orthosilicate, disodium orthosilicate, and the like.
Trisodium orthosilicate, tetrasodium orthosilicate, monosodium disilicate, disodium disilicate, trisodium trisilicate and monolithium orthosilicate can be mentioned.

The alkali metal salt of stannic acid is, for example, an acidic or neutral alkali metal salt of monostannous acid, and examples thereof include monosodium stannate and monolithium stannate. Can be mentioned.

The alkali metal salt of stannic acid is, for example, an acidic or neutral alkali metal salt of monostanic acid or a condensate thereof, and examples thereof include disodium monostannate (Na ₂ SnO ₃ .XH _2). O, x = 0
5), tetrasodium monostannate (Na ₄ SnO)
₄ ), β-stannic acid monosodium salt (Na ₂ O · 5Sn)
O ₂ · 8H ₂ O), Parasuzu disodium salt (Na _{2
Sn 5 O 11 · 2H 2 O} ), it may be mentioned Mesojisuzu disodium salt (Na ₂ SnO _5).

Germanium (II) acid (germanous acid)
Is an acidic or neutral alkali metal salt of monogermanic acid or a condensate thereof, and examples thereof include monosodium germanate (NaH).
GeO ₂ ).

Germanic acid (germanic acid)
Is, for example, an acidic or neutral alkali metal salt of monogermanic acid (IV) or a condensate thereof, and examples thereof include monolithium orthogermanate (LiH ₃ GeO ₄ ) disodium orthogermanate Tetrasodium orthogermanate, disodium digermanate (Na ₂ Ge ₂ O ₅ ),
Disodium tetragermanate (Na ₂ Ge ₄ O
₉ ), disodium pentagermanate (Na ₂ G
e ₅ O ₁₁ ), disodium metagermanate (Li
₂ Ge ₃ ), monosodium metadigermanate (NaH ₃ Ge ₂ O ₆ ), tetrasodium metadigermanate (Na ₄ Ge ₂ O ₆ ), and dinaturim pergermanate (Na ₂ Ge ₂ O ₇ ). be able to.

When the alkali metal salt of hypochlorous acid is monolead acid (mo
Noplumbous acid) is an acidic or neutral alkali metal salt, examples of which include sodium hypochlorite and potassium hypochlorite.

The alkali metal salt of lead acid is, for example, monolead acid.
Or neutral alkali metal salt of (monoplumbic acid)
And an example is Na_TwoPbO_Three, Na_TwoPb
_TwoO _Three, Na_TwoPb_FourO₉, Na_TwoPb_FiveO₁₁List
be able to.

(B) The alkali metal salt of an oxo acid of a metal element belonging to Group 14 of the periodic table reacts, for example, an oxo acid or oxide of a metal element belonging to Group 14 of the periodic table with a corresponding alkali metal compound. Can be prepared.

Examples of the oxo acid of the metal element belonging to Group 14 of the periodic table include, for example, silicic acid, stannic acid, stannic acid, germanic acid, hypochlorous acid and lead acid. Specific examples of these oxo acids will be apparent from the specific examples of the alkali metal salts of the above oxo acids.

Examples of the oxide of a metal element belonging to Group 14 of the periodic table include, for example, silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide, lead monoxide, lead dioxide and These condensates can be mentioned.

Further, as the alkali metal compound, preferred are, for example, alkali metal hydroxides, alkoxides, phenoxides, carbonates and carboxylate salts.

In the method of the present invention, (b) the alkali metal salt of an oxo acid of a metal element belonging to Group 14 of the periodic table can be directly added during the polycondensation reaction, and the oxo acid can be added according to the above-mentioned preparation reaction. In the case of preparing an alkali metal salt of an acid, an oxo acid or oxide and an alkali metal compound are separately added to a polycondensation reaction system, and (b) an oxo group metal element belonging to Group 14 of the periodic table is added in situ. Alkali metal salts of acids can also be formed.

When the alkali metal salt of oxo acid is prepared by the above-mentioned preparation reaction, it is preferable to use the oxo acid or oxide in a molar number larger than that of the alkali metal compound. When prepared in situ, the metal element of Group 14 of the periodic table of the oxo acid or oxide is preferably 50 moles (atoms) or less, more preferably 0.1 to 0.1 mole, per mole (atoms) of the alkali metal element of the alkali metal compound. 30 mol (atom)
When an oxo acid or an oxide and an alkali metal compound are used at a ratio such that an alkali metal salt of an oxo acid of a metal element belonging to Group 14 of the periodic table is formed in the polycondensation reaction system, Thus, a state is formed in which the cocatalyst described below is present in the polycondensation reaction system at a preferable ratio.

The above-mentioned polycondensation catalyst is preferably used when the alkali metal element in the polycondensation catalyst is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ equivalents per mole of the aromatic dihydroxy compound. A more desirable ratio is 5 × 10 for the same standard.
^-7 to 1 × 10 ^-5 equivalent.

In the polycondensation reaction of the present invention, together with the above-mentioned polycondensation catalyst, if necessary, at least one selected from the group consisting of an oxo acid of a metal element belonging to Group 14 of the periodic table and an oxide of the same metal element. One co-catalyst can coexist.

The oxo acids of Group 14 metal elements include, for example, silicic acid, stannic acid, stannic acid, germanic acid, hypochlorous acid and lead acid.

Examples of oxides of the metal elements belonging to Group 14 of the periodic table include silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide, lead monoxide, lead dioxide and condensates thereof. Can be mentioned.

The co-catalyst is preferably present in a proportion such that the metal element of Group 14 of the Periodic Table in the co-catalyst is 50 moles (atoms) or less per mole (atom) of the alkali metal element in the polycondensation catalyst. . If the co-catalyst is used in a proportion of more than 50 moles (atoms) of the same metal element, the rate of polycondensation reaction is undesirably reduced.

The cocatalyst is present in an amount such that the metal element of Group 14 of the periodic table of the cocatalyst is 0.1 to 30 mol (atoms) per 1 mol (atom) of the alkali metal element of the polycondensation catalyst. Is more preferred.

According to the study of the present inventor, when the above-mentioned polycondensation catalyst used in the present invention and the combination thereof with the co-catalyst are further coexisted with a nitrogen-containing basic compound, it is quite unexpected. It was found that the activity of the polycondensation catalyst was improved and side reactions were suppressed.

At this time, the nitrogen-containing basic compound acts as a cocatalyst for the polycondensation catalyst. As such a nitrogen-containing basic compound, for example, the following formula (III)

[0080]

Embedded image R ⁷ R ⁸ R ⁹ R ¹⁰ NX ² (III) wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, 6-20 cycloalkyl, cycloalkylalkyl, aryl or aralkyl groups, wherein X ² is OR ¹¹ , —OCOR ¹² ,
BR ₄ ¹³ or an F, R ¹¹ is 1 the number of hydrogen atoms or carbon
20 alkyl group, cycloalkyl of 6 to 20 carbon atoms, cycloalkyl alkyl, aryl or aralkyl group, R ¹² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, cycloalkyl having 6 to 20 carbon atoms , Cycloalkylalkyl, aryl or aralkyl groups;
¹³ is a hydrogen atom or an aryl group having 6 to 20 carbon atoms. ] Can be cited as preferable ones.

In the above formula (III), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 6 to 20 carbon atoms. , An aryl group or an aralkyl group.

The alkyl group having 1 to 20 carbon atoms may be linear or branched, and specific examples thereof include the same ones as exemplified for the above formula (II). it can.

Specific examples of the cycloalkyl group having 6 to 20 carbon atoms are the same as those exemplified for the above formula (II).

Examples of the cycloalkyl group having 6 to 20 carbon atoms include cycloalkyl having 5 to 12 carbon atoms and cycloalkyl having 5 to 12 carbon atoms.
Preferred are those comprising up to 15 linear or branched alkyls. Specific examples of such a cycloalkylalkyl group include, for example, cyclopentylmethyl, cyclohexylmethyl, and 3,4-dimethylcyclohexylmethyl.

Specific examples of the aryl group having 6 to 20 carbon atoms are the same as those exemplified for the above formula (II).

The aralkyl group having 6 to 20 carbon atoms includes, for example, aryl having 6 to 12 carbon atoms and aryl having 6 to 12 carbon atoms.
Those composed of 4 linear or branched alkyls are preferred. Specific examples of such an aralkyl group include, for example, benzyl, phenethyl and methylbenzyl.

In the formula (III), X ² represents —OR
¹¹ is a -OCOR ^12, BR ₄ ¹³ or F.

[0088] Therefore, the formula (III), when X ² is -OR ^11, formula (III) -1

[0089]

Embedded image R ⁷ R ⁸ R ⁹ R ¹⁰ NOR ¹¹ ... (III) -1 wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 have} the same definition as in formula (III). ].

Similarly, in the formula (III), X ² is —OCOR ¹²
In the case of the following formula (III) -2

[0091]

Embedded image R ⁷ R ⁸ R ⁹ R ¹⁰ NOCOR ¹² ... (III) -2 wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{12 have} the same definition as in formula (III). ].

In the formula (III), when X ² is —BR ¹³ , the following formula (III) -3

[0093]

Embedded image R ⁷ R ⁸ R ⁹ R ¹⁰ NBR ¹³ ... (III) -3 wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{13 have} the same definition as in formula (III). ].

Further, when X ² is F, the formula (III) represents the following formula (III) -4

[0095]

Embedded image R ⁷ R ⁸ R ⁹ R ¹⁰ NF (III) -4 wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are defined by the formula (II)
Same as I). ].

In the above formula (III) (including formulas (III) -1 to 4), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, cycloalkylalkyl. Group, an aryl group or an aralkyl group. Definition of R ¹² is the same as the definition of R ^11. R ¹³ is a hydrogen atom or an aryl group having 6 to 20 carbon atoms. R ¹¹ ,
Specific examples of each of the above groups in the definition of R ¹² and R ¹³ include the same as those exemplified for the formula (II).

The compound represented by the formula (III) -1 includes, for example, teratomethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, tetraethylammonium hydroxide, propyltolumethylammonium hydroxide Butyltrimethylammonium hydroxide, dibutyldiethylammonium hydroxide, tributylpropylammonium hydroxide, tetrabutylammonium hydroxide, dimethylethylpentylammonium hydroxide, hexyltrimethylammonium hydroxide, hexyltriethylammonium hydroxide, hexyltributylammonium hydroxide, Dihexyl dimethyl ammonium hydroxide, Nonyltripropylammonium hydroxide, nonyldiethylpentylammonium hydroxide, decyltrimethylammonium hydroxide, tetrakis (decyl) ammonium hydroxide,
Tetradecyltrimethylammonium hydroxide, tetradecyldimethylethylammonium hydroxide,
Tetradecyldiethylbutylammonium hydroxide, bis (tetradecyl) dimethylammonium hydroxide, bis (tetradecyl) ethylnonylammonium hydroxide, tris (tetradecyl) methylammonium hydroxide, tris (tetradecyl) propylammonium hydroxide, tris (tetradecyl) nonyl Ammonium hydroxide, tetrakis (tetradecyl) ammonium hydroxide, hexadecyltrimethylammonium hydroxide, hexadecyltripropylammonium hydroxide, bis (hexadecyl)
Diethylammonium hydroxide, hexadecyltributylammonium hydroxide, hexadecyldimethylhexylammonium hydroxide, bis (hexadecyl) dimethylammonium hydroxide, tetrakis (hexadecyl) ammonium hydroxide; cyclohexyltrimethylammonium hydroxide, cyclopentyltributylammonium hydroxide, bis (Cyclohexyl) methylethylammonium hydroxide, tris (cyclopentyl) methylammonium hydroxide, tetrakis (cyclohexyl) ammonium hydroxide; phenyltrimethylammonium hydroxide, phenyldimethylethylammonium hydroxide, phenylnonyldecylmethylammonium hydroxide, benzyloxide Ammonium hydroxide, benzyl dimethyl ammonium hydroxide, p- tolyl triethylammonium hydroxide,
m-xylyltripropylammonium hydroxide,
Diphenyldimethylammonium hydroxide, phenylnonyldimethylammonium hydroxide, 1-naphthyltrimethylammonium hydroxide, p-biphenyltriethylammonium hydroxide, 2-naphthyltripropylammonium hydroxide, phenylcyclohexyldimethylammonium hydroxide, phenyl 2-naphthyldiethyl Ammonium hydroxide;
Tetramethylammonium methoxide, tetramethylammonium ethoxide, tetramethylammonium n-
Propoxide, tetramethylammonium i-propoxide, tetramethylammonium n-butoxide, tetramethylammonium phenoxide, tetraethylammonium methoxide, tetraethylammonium ethoxide, ethyltrimethylammonium methoxide, ethyltrimethylammonium ethoxide, tetran-propylammonium Methoxide, tetra-n-propylammonium ethoxide, tetrabutylammonium methoxide, tetrabutylammonium ethoxide, tetrabutylammonium i-propoxide, tri-n-butylethylammonium methoxide, tetrahexylammonium ethoxide, tetrahexylammonium iso Propoxide, benzyltrimethylammonium methoxide, benzyltrime It can be exemplified Le ammonium ethoxide and benzyltriethylammonium methoxide.

Of these, the compound represented by R ⁷ (CH ₃ ) ₃ NOH is preferred because of its high catalytic activity.

Examples of the compound represented by the formula (III) -2 include tetramethylammonium acetate, tetramethylammonium hexanecarboxylate, tetramethylammonium nonanecarboxylate, tetramethylammonium hexadecanecarboxylate, tetramethylammonium cyclohexanecarboxylate, Tetramethyl ammonium benzene carboxylate, tetramethyl ammonium 2-naphthalene carboxylate, ethyl trimethyl ammonium ethane carboxylate, dimethyl diethyl ammonium butane carboxylate, tetraethyl ammonium octane carboxylate, propyl triethyl ammonium tetradecane carboxylate, dibutyl diethyl ammonium 1-naphthalene carb Ruboxylate, tributyl propyl ammonium cyclopentane carboxylate, tetrabutyl ammonium acetate, tetrabutyl ammonium benzene carboxylate, pentyl dimethyl ethyl ammonium butane carboxylate, hexyl trimethyl ammonium oleate, hexyl trimethyl ammonium hexadecane carboxylate, hexyl triethyl ammonium cyclohexane carboxylate, hexyl Tributyl ammonium ethane carboxylate, dihexyl dimethyl ammonium hexane carboxylate, bis (nonyl tripro ammonium) succinate, bis (nonyl diethyl pentyl ammonium) adipate, bis (decyl trimethyl ammonium) terephthalate, tetrakis (decyl) Ammonium cyclohexanecarboxylate, tetradecyltrimethylammonium tetradecanecarboxylate, tetradecyldimethylethylammonium p-dodecylbenzenecarboxylate, tetradecyldiethylbutylammonium acetate, bis (tetradecyl) dimethylammoniumpentanecarboxylate, bis (tetradecyl) ethylnonylammoniumdecane Carboxylates, tris (tetradecyl) methylammonium octadecanecarboxylate, tetrakis (tetradecyl) ammonium acetate, tetrakis (tetradecyl) ammonium formate, hexadecyltrimethylammonium cyclohexanecarboxylate, hexadecyltrimethylammonium 1-pyridinecarboxylate , Hexadecyltrimethylammonium propyl ammonium 2-pyridinecarboxylate, bis (hexadecyl) diethylammonium 4-chlorobenzene-carboxylate,
Hexadecyltributylammonium 2,4-cybutylbenzenecarboxylate, hexadecyldimethylhexylammonium 6-methyl-2-naphthalenecarboxylate, bis (hexadecyl) dimethylammoniumquinolinecarboxylate, tetrakis (hexadecyl)
Ammonium acetate, cyclohexyltrimethylammonium formate, cyclopentyltributylammonium butanecarboxylate, bis (cyclohexyl) methylethylammonium octanecarboxylate, tris (cyclopentyl) methylammonium dodecanecarboxylate, tetrakis (cyclohexyl)
Ammonium cyclohexanecarboxylate, phenyltrimethylammonium formate, phenyltrimethylammonium acetate, phenyltrimethylammonium decanecarboxylate, phenyltrimethylammonium hexadecanecarboxylate, phenyltrimethylammonium benzenecarboxylate, phenyltrimethylammonium 1-pyridinecarboxylate, phenyldimethylethylammonium 2-naphthalenecarboxylate, phenylnonyldecylmethylammoniumbenzenecarboxylate, benzyltrimethylammonium hexadecanecarboxylate, benzyldimethylpropylammoniumoctanecarboxylate, p-tolyltriethylammonium acetate, m-xylyl Ripropylammonium pentanecarboxylate, bis (diphenyldimethylammonium) fumarate, bis (phenylnonyldimethylammonium) oxalate, tris (1-naphthyltrimethylammonium) trimellitate, p-biphenyltriethylammonium acetate, 2-naphthyltripropylammonium cyclobutanecarboxylate And phenylcyclohexyldimethylammonium decanecarboxylate.

The compound represented by the formula (III) -2 is easy to handle because of its high catalytic activity and high stability.
preferable.

Examples of the compound represented by the formula (III) -3 include tetramethylammonium borohydride, ethyltrimethylammonium borohydride, dimethyldiethylammonium borohydride, tetraethylammonium borohydride, butyltrimethylammonium borohydride, butylpropylethylmethyl Ammonium borohydride, dibutyldiethylammonium borohydride, tetrabutylammonium borohydride, hexyltrimethylammonium borohydride, hexyltriethylammonium borohydride, hexyltributylammonium borohydride, dihexyldimethylammonium borohydride, nonyltripropylammonium borohydride, nonyldiethylpentyl Ammonium borohydride, decyl Trimethylammonium borohydride, tetrakis (decyl) ammonium borohydride,
Tetradecyltrimethylammonium borohydride, tetradecyldimethylammonium borohydride, tetradecyldiethylbutylammonium borohydride, bis (tetradecyl) dimethylammonium borohydride,
Bis (tetradecyl) ethylnonyl ammonium, tris (tetradecyl) methyl ammonium borohydride,
Tris (tetradecyl) propylammonium borohydride, tris (tetradecyl) nonylammonium borohydride, tetrakis (tetradecyl) ammonium borohydride, hexadecyltrimethylammonium borohydride, hexadecyltripropylammonium borohydride, bis (hexadecyl) diethylammonium borohydride, Hexadecyltributylammonium borohydride, hexadecyldimethylhexylammonium borohydride, bis (hexadecyl) dimethylammonium borohydride, tetrakis (hexadecyl) ammonium borohydride, cyclohexyltributylammonium borohydride, cyclopentyltributylammonium borohydride, bis (cyclohexyl) methylethyl Ammoniu Borohydride, tris (cyclopentyl) ethylammonium borohydride, tetrakis (cyclohexyl) ammonium borohydride, phenyltrimethylammonium borohydride, phenyldimethylethylammonium borohydride, phenylnonyldecylmethylammonium borohydride, benzyltrimethylammonium borohydride, benzyldimethyl Propylammonium borohydride, p-tolyltriethylammonium borohydride, m-xylyltripropylammonium borohydride, diphenyldimethylammonium borohydride, phenylnonyldimethylammonium borohydride, 1-naphthyltrimethylammonium borohydride, p-biphenyltriethylammonium borohydride , 2-Naphtilt Propyl ammonium borohydride, phenylcyclohexyl dimethyl ammonium borohydride, phenyl 2-naphthyl diethyl ammonium borohydride; tetramethyl ammonium tetraphenyl borate, tetramethyl ammonium triphenyl benzyl borate, tetraethyl ammonium tetraphenyl borate, tetraethyl ammonium triphenyl benzyl borate, triethyl Methyl ammonium tetraphenyl borate, dimethyl diethyl ammonium tetraphenyl borate, tetra n-propyl ammonium tetraphenyl borate, tetra n
-Butylammonium tetraphenylborate, tetra-n-propylammonium dibenzyldiphenylborate, tri-n-propylmethylammonium tetraphenylborate, tri-n-butylethylammonium tetraphenylborate, tetra-n-hexylammonium tetraphenylborate, cyclohexyltrimethylammonium tetra Mention may be made of phenylborate, cyclohexyltriethylammonium tetraphenylborate and phenyltrimethylammonium tetraphenylborate.

Of these, tetramethylammonium tetraphenylborate and tetraphenylammonium tetraphenylborate are preferred.

Examples of the compound represented by the formula (III) -4 include tetramethylammonium fluoride, ethyltrimethylammonium fluoride, diethyldimethylammonium fluoride, tetraethylammonium fluoride, n-propyltriethylammonium fluoride, n-propyltriethylammonium fluoride and n-propyltriethylammonium fluoride.
-Butyltrimethylammonium fluoride, tetra-n-
Butylammonium fluoride, hexyltrimethylammonium fluoride, hexyltriethylammonium fluoride, decyltrimethylammonium fluoride, cyclohexyltrimethylammonium fluoride, cyclopentyltrimethylammonium fluoride, cyclohexyltributylammonium fluoride, bis (cyclohexyl) dimethylammonium fluoride, Tetrakis (cyclohexyl) ammonium fluoride, phenyltrimethylammonium fluoride, phenyltriethylammonium fluoride, phenyldimethylethylammonium fluoride, benzyltrimethylammonium fluoride,
Examples thereof include m-xylyltrimethylammonium fluoride, 1-naphthyltrimethylammonium fluoride and 2-naphthyltrimethylammonium fluoride.

When the nitrogen-containing basic compound is used alone as a polycondensation catalyst without being used together with the above-mentioned polycondensation catalyst containing a metal element of Group 14 of the periodic table, the polycondensation temperature of the polycarbonate is 200. ℃, especially when it exceeds 250 ℃
Usually, the activity of the polycondensation catalyst rapidly decreases, but in the catalyst system of the present invention, the presence of the nitrogen-containing basic compound significantly improves the catalyst activity.

The nitrogen-containing basic compound is preferably used in such a ratio that the amount of ammonium nitrogen atoms in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ equivalent per mole of the aromatic dihydroxy compound. . A more preferable ratio is a ratio that is 2 × 10 ^{−5 to} 7 × 10 ⁻⁴ equivalents with respect to the same standard. A particularly desirable ratio is 5 × 10 ⁻⁵ to 5 with respect to the same standard.
× 10 ⁻⁴ equivalent.

In the process of the present invention, the polycondensation catalyst, cocatalyst and cocatalyst are added together or separately into the polycondensation reaction system, preferably before the start of the polycondensation. These catalysts, cocatalysts and cocatalysts can be added as they are or in a state of being dissolved or suspended in an inert medium. The solution or suspension preferably contains these catalysts and the like at a solid content of 30% by weight or less, more preferably 20% by weight or less.

Furthermore, the concentration of oxygen dissolved in these solutions or suspensions is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less.
ppm or less is preferred. If it exceeds this range, coloring or branched components are likely to be generated due to the influence of dissolved oxygen.

In the present invention, it is preferable to add various stabilizers in a molten state at least one time before, during or after the polymerization. Examples of the stabilizer include a sulfur-containing acidic compound and / or a derivative formed from the acidic compound, a phenol-based stabilizer, a thioether-based stabilizer, a phosphorus-based stabilizer, a hindered amine-based stabilizer, an epoxy compound, a salicylic acid-based ultraviolet absorber, Benzotriazole ultraviolet absorbers and the like can be mentioned.

Examples of the sulfur-containing acidic compound and / or the derivative formed from the acidic compound include sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds, and derivatives thereof. As sulfuric acid derivatives, for example, diethyl sulfate, dipropyl sulfate,
Examples thereof include dibutyl sulfate, diethyl sulfite, sodium dodecyl sulfate, sodium hexadecyl sulfate, dimethyl butyl tridecyl ammonium butyl sulfate, dimethyl ethyl hexadecyl ammonium ethyl sulfate, and trimethyl decyl ammonium methyl sulfate.

Examples of the sulfinic acid compound include, for example,
Toluenesulfinic acid, naphthalenesulfinic acid and the like can be mentioned. Examples of the sulfonic acid compounds and derivatives thereof include sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid; methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, and phenylbenzenesulfonate. , P-methyl toluenesulfonate, p-
Sulfonates such as ethyl toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; and ammonium p-toluenesulfonate, tetrabutylphosphonium p-toluenesulfonate, dodecylbenzene Sulfonates such as tetraphenylphosphonium sulfonate can be mentioned.

These compounds can be used alone or in combination. Among them, a sulfur-containing acidic compound having a pKa value of 3 or less and a derivative formed from the acidic compound, and a sulfonic acid compound and this derivative are preferably used. In particular, benzenesulfonic acid, butylbenzenesulfonic acid, -Toluenesulfonic acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, sodium dodecyl sulfate, trimethyl methyl sulfate, hexadecylammonium, tetrabutylphosphonium p-toluenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate are preferably used. Can be

Examples of the phenol-based stabilizer include, for example, n
-Octadecyl-3- (4-hydroxy-3 ', 5'-
Di-tert-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-)
Hydroxyphenyl) propionate] methane, 1,
1,3-Tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzylmalonate, 4-hydroxymethyl-2,6-di-t-butylphenol and the like. These may be used alone or as a mixture of two or more.

As the thioether-based stabilizer, for example,
Dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate Pionate) and the like. These may be used alone or as a mixture of two or more.

Examples of the phosphorus-based stabilizer include bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite, diphenyldecyl phosphite, and the like.
Arylalkyl phosphites such as phenylisooctyl phosphite and 2-ethylhexyl diphenyl phosphite; trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, and tris (2-chloroethyl ) Trialkyl phosphites such as phosphite and tris (2,3-dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) Phosphite, tris (2,4-di-t
Tributyl phosphite, tris (hydroxyphenyl) phosphite, and other triaryl phosphites; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl phosphate, tris (2-chloroethyl) phosphate, etc. Trialkyl phosphates; tricycloalkyl phosphates such as tricyclohexyl phosphate; triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, and 2-ethylphenyl diphenyl phosphate. These may be used alone or as a mixture of two or more.

The hindered amine stabilizers include:
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-benzyl-7,7,9,9
-Tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, tetrakis (2,2 , 6,6-tetramethyl-4
-Piperidyl) 1,2,3,4-butanetetracarboxylate. Even if these are used alone,
You may mix and use more than one kind.

In the present invention, an epoxy compound can be used as a stabilizer. As such an epoxy compound, a compound having one or more epoxy groups in one molecule is preferably used.

Specific examples of such epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-
3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylsilohexylcarboxy Rate, bisphenol-A diglycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide , Tetraphenylethylene epoxide, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxy Cyclohexane, 3-methyl -
5-t-butyl-1,2-epoxycyclohexane and the like.

Examples of the salicylic acid type ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-
Carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-
Hydroxy-4-n-octyloxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-methoxybenzophenone-5 —Sulfonic acid and the like.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl) -Phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di -T
-Butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4",
5 ", 6" -tetrahydrophthalimidomethyl) -5 '
-Methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2-benzotriazol-2-yl) phenol] and the like. .

Examples of cyanoacrylate-based ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3-
Diphenyl acrylate, ethyl-2-cyano-3,3
-Diphenyl acrylate and the like.

These various stabilizers are used in an amount of 10 ^-8 to 10 based on 1 mol of the aromatic dihydroxy compound as a raw material.
^-1 mol, preferably 10 ^-7 to 10 ^-2 mol, is used.

In the method of the present invention, the polycondensation reaction system is preferably used as a terminal blocking agent for the main polycarbonate in a polycondensation reaction system, preferably having 10 to 40 carbon atoms, more preferably 15 to 40 carbon atoms.
Is preferably 0.05 to 10 mol%, more preferably 0.1 to 10 mol%, based on the aromatic dihydroxy compound.
It is used in an amount of 5 to 7 mol%, more preferably 1 to 5 mol%.

The phenols having 10 to 40 carbon atoms include, for example, on-butylphenol, p-cyclohexylphenol, o-phenylphenol, m-isobutylphenol, mn-nonylphenol, pt-
Butylphenol, om-pentylphenol, p-
Cumylphenol, pn-pentylphenol, o-
Naphthylphenol, pn-pentylphenol, m
-N-hexylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5
Monovalent phenols such as monohydroxychroman derivatives such as di-t-butylphenol, 2,6-dicumylphenol, 3,5-dicumylphenol, and 2,2,2-trimethyl-4- (hydroxyphenyl) chroman Is used.

In the method of the present invention, the polycondensation reaction between the aromatic dihydroxy compound and the diaryl carbonate can be performed under the same conditions as conventionally known polycondensation reaction conditions.

Specifically, the first-stage reaction was carried out at 80 to 25.
At a temperature of 0 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C., 0.5 to 5 hours, preferably 1 to 4 hours, more preferably 1.5 to 3 hours, under reduced pressure, aromatic A dihydroxy compound is reacted with a diaryl carbonate. Next, the reaction temperature was increased while increasing the degree of vacuum in the reaction system, and the reaction between the aromatic dihydroxy compound and the diaryl carbonate was carried out.
Hg or less, preferably 1 mmHg or less under reduced pressure, 24
A polycondensation reaction between the aromatic dihydroxy compound and the diaryl carbonate is performed at 0 to 320 ° C.

The above-mentioned polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The polycarbonate as a reaction product obtained as described above usually has an intrinsic viscosity (methylene chloride solution) measured at 20 ° C. of preferably 0.1 to 10%.
1.0, more preferably 0.2 to 0.8.

In the present invention, a mold release agent, a colorant, an antistatic agent, a lubricant, an antifogging agent, a natural oil, a synthetic oil, and the like may be added to the polycarbonate obtained as described above as long as the object of the present invention is not impaired. Waxes, organic fillers, inorganic fillers and the like can be added.

According to the present invention, it is possible to produce a polycarbonate having a good polymer color tone, suppressing side reactions, and producing less insoluble matter and foreign matter due to a branching reaction even when the polymerization degree is high. In addition, branching reactions and other side reactions are also suppressed during molding processing, causing burns, coloring, insolubilization, generation of foreign matter,
It is possible to obtain a polycarbonate in which a decrease in the molecular weight is suppressed to a low level.

Further, according to the method of the present invention, a high-quality polycarbonate as described above can be efficiently produced with high productivity. Further, according to the method of the present invention, without washing the polymerization apparatus for a long time, even if it is used repeatedly,
The method of the present invention is very advantageous as a method for industrially producing polycarbonate, because the high-quality polycarbonate as described above can be continuously produced.

As described above, the advantages of the method of the present invention are basically the above-mentioned polycondensation catalyst used by the present inventors, the combination of the polycondensation catalyst and the co-catalyst, and further, the combination of the polycondensation catalyst and the cocatalyst. Is achieved by a combination of

Therefore, according to the present invention, it is selected from the group consisting of (a) an alkali metal salt of an ate complex of a metal element belonging to Group 14 of the periodic table and (b) an alkali metal salt of oxo acid of the same metal element. At least one alkali metal salt,
Here, the metal element of Group 14 of the periodic table is selected from the group consisting of silicon, germanium, tin and lead. A polycondensation catalyst for a polycarbonate comprising: a catalyst comprising a combination of the polycondensation catalyst and at least one cocatalyst selected from the group consisting of oxo acids of metal compounds of Group 14 of the periodic table and oxides of the same metal elements. And a catalyst comprising the above-mentioned polycondensation catalyst or a combination of the above-mentioned polycondensation catalyst and a co-catalyst with a nitrogen-containing basic compound as a cocatalyst.

[0133]

According to the present invention, it is possible to produce an aromatic polycarbonate which is free from coloring and has few branches and insolubilized substances by a melt polymerization method. That is, according to the present invention, a side reaction such as a branching reaction at the time of molding is suppressed, and burnt, colored, insolubilized, and
It is possible to produce an aromatic polycarbonate in which generation of foreign matter and reduction in molecular weight are suppressed.

According to the present invention, an aromatic polycarbonate can be produced at a high polymerization rate with high productivity.

[0135]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified. In the examples, evaluation of physical properties and the like was performed according to the following methods.

(I) Intrinsic viscosity [η]: Measured in methylene chloride at 20 ° C. with an Ubbelohde viscometer.

(Ii) Filterability and foreign matter generation: SUS31
In a 6 tester, the polymer was treated at 290 ° C. under a stream of nitrogen for 2.0 hours. The obtained polymer is pulverized and 5 g
Was added to 100 ml of methylene chloride, and the mixture was dissolved by ultrasonic irradiation. The polymer solution was filtered with a 1 micron pore filter under a pressure of 0.5 kg / cm ² . Filterability is
"Good" ... Filtration in less than 15 minutes, "Somewhat bad" ... 15-30
Filtration in minutes, "poor" ... filtration time exceeds 30 minutes, 3
It was evaluated on a scale. Black foreign matter remaining on the filter
"Small": Less than 10 pieces, "Medium": 10-20 pieces, "More" ...
The evaluation was made in three steps of exceeding 20 pieces.

(Iii) Polymer color tone: L value and b value:
An injection molded plate having a thickness of 3 mm is molded at a cylinder temperature of 300 ° C and an injection pressure of 100 kg / cm ^{2 at a} mold temperature of 90 ° C.
Y and Z values are calculated by Color Colo manufactured by Nippon Denshoku Industries
r Reference Meter ND-100
The L value and the b value were measured by the transmission method at 1 DP.

(Iv) Gel evaluation 10 g of the polymer was placed in a stainless steel container, and 290 ° C. /
After heat treatment under a condition of 0.3 to 0.5 mmHg / 20 hours, the resulting product was dissolved in 500 to 1000 ml of methylene chloride to collect insoluble components. The dry weight of the insoluble portion is expressed as a percentage by weight based on the weight of the sample before dissolution.

(V) Polymerization activity: Intrinsic viscosity [η] is 0.1.
The polymerization time (t) at which the temperature reached 45 was measured. Productivity is 24
Expressed in time / t (time).

Examples 1-38 Bisphenol A22
8 parts, 225 parts of diphenyl carbonate and Tables 1-1
A catalyst of the type and amount shown in No. 3 was charged into a reaction tank (capacity: 100 liters) equipped with a stirrer, a still and a decompressor, and the atmosphere was replaced with nitrogen. After stirring for 30 minutes, the internal temperature was raised to 180 ° C., and the pressure was gradually reduced to 100 mm
The reaction was carried out for 30 minutes with Hg, and the phenol produced was distilled off. The pressure was gradually reduced while the temperature was raised to 200 ° C.
The reaction was carried out while distilling out phenol with Hg for 30 minutes to perform a transesterification reaction.

Next, the reaction solution was transferred to the second reaction tank,
The temperature was gradually increased and reduced to 20 ° C. and 30 mmHg, and the pressure was reduced at the same temperature and pressure for 30 minutes.
The temperature and pressure were repeatedly increased and reduced to 1 mmHg at 270 ° C. and 1 mmHg or less in the same procedure as above to continue the reaction.

Then, the polymerization was carried out by appropriately sampling while measuring the stirring power at 270 ° C. and 1 mmHg, and polymerizing [η] =
The polymerization time to obtain 0.45 was determined, and finally [η] = 0.
The polycondensation was carried out to 5 to produce a polycarbonate resin.

Table 1 shows the physical properties of these polycarbonate resins.
~ 13. In the table, (* 1) is represented by the molar equivalent of alkali metal to 1 mol of BPA. (* 2) is represented by the molar equivalent of the Group 14 element to 1 mol of BPA.
(* 3) is represented by the molar equivalent of alkali metal to 1 mol of BPA. (* 4) is represented by the molar equivalent of the nitrogen-containing basic compound to 1 mol of BPA. (* 1) ~
(* 4) has the same meaning in Tables 2 to 14.

In Examples 10, 11, 12, 25, and 26, the Group 14 element compound and the alkali metal compound were previously mixed at room temperature to prepare a catalyst, and then added to the reaction tank. On the other hand, in Examples 13, 14, 27, and 28, a Group 14 element compound component and an alkali metal compound were separately added to a reaction vessel, and a catalyst was prepared in the reaction vessel.

Example 39 Bisphenol A 228
Parts, 181.9 parts of diphenyl carbonate and 95.4 parts of diphenyl isophthalate were charged into the reaction vessel described in Example 1 together with the catalyst shown in Table 14 and then replaced with nitrogen. After stirring for 30 minutes, gradually reduce the pressure
The pressure was set to 00 mmHg, and the reaction was carried out at the same pressure for 30 minutes. Under the same pressure, the internal temperature was gradually raised to 180 ° C. The reaction was carried out at the same temperature and pressure for 1 hour. While gradually increasing the degree of decompression,
The internal temperature was also gradually increased to reach 30 mmHg and 200 ° C. Phenol was distilled off at the same temperature and pressure for 1 hour to carry out a transesterification reaction.

The obtained reaction product was sent to an adjacent polymerization tank of the same type, and polycondensation and reaction were continued under the same conditions as in Example 1 until η = 0.5. Table 14 shows the polymerization activity and physical properties of the obtained polymer.

[0148]

[Table 1]

[0149]

[Table 2]

[0150]

[Table 3]

[0151]

[Table 4]

[0152]

[Table 5]

[0153]

[Table 6]

[0154]

[Table 7]

[0155]

[Table 8]

[0156]

[Table 9]

[0157]

[Table 10]

[0158]

[Table 11]

[0159]

[Table 12]

[0160]

[Table 13]

[Comparative Examples 1 to 4] Polycarbonates were produced in the same manner as in Example 1 except that the catalysts shown in Table 9 were used. Table 9 shows the polymerization activity and physical properties of the obtained polymer.

The polycarbonate produced according to the present invention produced little insoluble foreign matter and could be filtered quickly. on the other hand,
According to the comparative example, many gel-like foreign substances were found on the filter during filtration. According to the present invention, when the color tone evaluation injection molded plate is molded, when the molding is completed and then the molding is restarted, the number of visually generated black foreign substances has been kept at a low level.

[0163]

[Table 14]

Continuing from the front page (72) Inventor Shigeru Hirata 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Pref. Teijin Co., Ltd. (72) Inventor Masanori Abe 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Pref. Teijin Limited Iwakuni Research Center (56) References JP-A-5-148355 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (8)

(57) [Claims] 1. An aromatic dihydroxy compound and a diaryl carbonate are composed of (a) an alkali metal salt of an ate complex of a metal element belonging to Group 14 of the periodic table and (b) an alkali metal salt of an oxo acid of the same metal element. At least one alkali metal salt selected from the group
A method for producing an aromatic polycarbonate, characterized in that polycondensation is carried out using a polycondensation catalyst wherein the metal element of the group is selected from the group consisting of silicon, germanium, tin and lead. (A) An alkali metal salt of an ate complex of a metal compound of Group 14 of the periodic table is represented by the following formula (II): M ¹ M ² X ¹ _p (OR ⁶ ) _q (II) [Where M ¹ is an alkali metal, M ² is silicon,
Germanium, tin or lead, and X ¹ has 1 to ¹ carbon atoms.
An alkyl group having 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms or a carbon number. 6 to 20 aryl groups, p and q are 0 or an integer of 1 to 5, provided that p + q is 3
Or 5. The method according to claim 1, which is represented by the following formula: (B) an alkali metal salt of an oxo acid of a metal element belonging to Group 14 of the periodic table is an alkali metal salt of silicic acid;
Alkali metal salts of stannic acid, alkali metal salts of stannic acid,
The method according to claim 1, wherein the method is selected from the group consisting of alkali metal salts of germanate (II), alkali metal salts of germanate (IV), alkali metal salts of hypochlorous acid and alkali metals of lead acid. 4. The method according to claim 1, wherein the polycondensation is carried out in the presence of at least one cocatalyst selected from the group consisting of an oxo acid of a metal element belonging to Group 14 of the periodic table and an oxide of the same metal element. Method. 5. The oxo acid of a metal element belonging to Group 14 of the Periodic Table used as a co-catalyst is selected from the group consisting of silicic acid, stannic acid, stannic acid, germanic acid, hypochlorous acid and lead acid. 4. The method according to 4. 6. The oxide of a metal element belonging to Group 14 of the periodic table is composed of silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide, lead monoxide, lead dioxide, and a condensate thereof. 5. The method of claim 4, wherein the method is selected from the group consisting of: 7. The co-catalyst according to claim 4, wherein the co-catalyst is present in a proportion such that the metal element of Group 14 of the periodic table in the co-catalyst is not more than 50 mol per mol of the alkali metal element in the polycondensation catalyst. Method. 8. The process according to claim 1, wherein a nitrogen-containing basic compound is present as a cocatalyst.