JPH08302004A - Polycarbonate and its production - Google Patents

Abstract

PURPOSE: To obtain a polycarbonate polymer which has a reduced amount of matter soluble in acetone, comprises specific chain terminals and recurring units, maintains high heat stability and resistance to water, shows excellent flowability in molding and is useful for molded products widely applicable to electric and electronic purposes. CONSTITUTION: This polycarbonate resin contains <=3 mole % of soluble matter in acetone and comprises the recurring units given in formula I (R<1> and R<2> are each a halogen, a 1-8C alkyl; R<3> and R<4> are each H, a 1-7C alkyl; m and n are each 0-4) as the main chains and the group of formula II (R is an 8-30C alkyl) as terminal groups in an amount of 5-95 mole % based on the whole terminal groups. This resin is produced by effecting the transesterification reaction between a dihydroxy compound and a carbonic diester, melt-admixing a 8-30C long-chain alkyl alcohol to the reaction mixture at the time when the degree of the conversion exceeds 50% followed by polycondensation reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate and a method for producing the same, more specifically, a novel polycarbonate having excellent fluidity, thermal stability and water resistance, and a dihydroxy compound and a carbonate. The present invention relates to a method for producing by a transesterification reaction with a diester.

[0002]

2. Description of the Related Art Polycarbonate is an engineering plastic excellent in transparency, heat resistance or impact resistance, and is currently widely used in the electric / electronic field, automobile field, optical component field and other industrial fields. The above-mentioned polycarbonate is generally molded by various molding methods such as extrusion molding, injection molding and melt molding, and is used for various purposes. However, since polycarbonate generally has a higher melt viscosity of resin than other polymers, it is usually molded at a high temperature of about 300 ° C. in order to obtain sufficient fluidity. Especially when molding thin-walled products or complicated shapes,
Since the resin does not have sufficient fluidity, it is necessary to perform molding at a higher temperature. When molding at such a high temperature, thermal decomposition of the polycarbonate resin is likely to occur,
The resin may be colored by thermal oxidation. Further, the hydrolysis of the main chain causes a decrease in the molecular weight, which may cause a decrease in strength of the molded product and a poor appearance. Therefore, there has been a demand for a method capable of improving fluidity while satisfying thermal stability and water resistance. As a method of improving fluidity, for example, a method of introducing a long-chain alkyl group into the main chain or the terminal is well known. As such a method, for example, a method of introducing a long-chain alkyl group at the terminal position (Japanese Patent Publication No. 52-50078), or a method of reacting dodecanedioic acid or the like to introduce an alkyl group into the main chain (Japanese Patent Laid-Open No. Hei 10 (1999) -58242) No. 3-212424), but all of these methods have a drawback that the obtained molded product has low thermal stability. Further, a method in which an aliphatic monocarboxy compound or a long-chain alkyl alcohol is added at the time of polymerization to introduce an alkyl group at the terminal (JP-A-63-92643, JP-A-5-92).
No. 83), but in the above method, a large amount of low molecular weight substances are produced, resulting in the problem of poor water resistance and heat resistance. That is, a polycarbonate which satisfies all requirements of fluidity, thermal stability and water resistance has not been obtained by any method.

[0003]

The present invention has been made under such circumstances. That is, the present invention
An object of the present invention is to provide a polycarbonate having excellent fluidity while maintaining the excellent thermal stability and water resistance that the polycarbonate originally has, and to provide a method for producing the polycarbonate.

[0004]

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the above-mentioned object of the present invention was to identify a main chain composed of a specific repeating unit and a specific end group. In addition, the long-chain alkyl alcohol is melted when the reaction rate exceeds a certain value in a transesterification reaction using a polycarbonate that has an acetone-soluble content below a certain value, and in a transesterification reaction using a dihydroxy compound and a carbonic acid diester. It was found that this can be achieved by a method for producing a mixed polycarbonate. The present invention has been completed based on such findings. That is, the present invention provides (1)
Repeating unit (I)

[0005]

Embedded image

(In the formula, R ¹ and R ² each represent a halogen atom or an alkyl group having 1 to 8 carbon atoms, and m and n
Each represents an integer of 0 to 4. Also, R ³ and R ⁴
Each represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ), And 5 to 95 mol% of all end groups have the general formula (II)

[0007]

[Chemical 4] (In the formula, R ¹ , R ² , R ³ , R ⁴ , m and n have the same meanings as those in the above general formula (I), and R represents an alkyl group having 8 to 30 carbon atoms.)

[0008] A polycarbonate represented by the following formula, wherein the acetone-soluble content is 3 mol% or less, and (2) a polycarbonate is produced by a transesterification reaction using a dihydroxy compound and a carbonic acid diester. In doing so, when the reaction rate of the dihydroxy compound and the carbonic acid diester reaches a value of 50% or more, a long-chain alkyl alcohol is melt-mixed, and polycondensation is provided. is there.

The present invention will be described in more detail below. The polycarbonate of the present invention has a main chain composed of a repeating unit represented by the above general formula (I). In the above general formula (I), R ¹ and R ² are each a halogen atom such as fluorine, chlorine, bromine or iodine or a carbon number of 1 to 8
Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
The sec-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, hebutyl group, octyl group and the like are shown. R ¹ and R ² may be the same or different. Further, a plurality if R ¹ is more R ¹
It may be the same or different, a plurality of R ² if R ² there are a plurality may be the same or different. m and n
Are integers of 0 to 4, respectively. In the present invention,
Those in which both m and n are 0 are particularly preferable.
R ³ and R ⁴ are each a hydrogen atom or a carbon number 1
To 7 alkyl groups, and examples of the alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group and a propyl group. The above R ³ and R ⁴ may be the same or different from each other. In the present invention, R ³ and R
Particularly preferred are those in which all ⁴ are methyl groups.

In the polycarbonate of the present invention, 5 to 95 mol% of all terminal groups, preferably 20 to 95
Mol%, more preferably 30 to 95 mol%, is a group represented by the general formula (II). When this ratio is less than 5 mol%, sufficient fluidity cannot be obtained, and when it exceeds 95 mol%, a large amount of low molecular weight substances are by-produced, which is not preferable. General formula (II)
In the above, the alkyl group having 8 to 30 carbon atoms represented by R may be linear or branched, and is preferably an alkyl group having 12 to 24 carbon atoms. When R is an alkyl group having a carbon number outside the above range, that is, when the carbon number is less than 8, the effect of improving fluidity is not recognized, and when the carbon number exceeds 30, the reactivity is insufficient. Yes,
It becomes difficult to introduce it at the end.

Furthermore, the polycarbonate of the present invention has an acetone-soluble content of 3 mol% or less. If this value exceeds 3 mol%, the water resistance is poor, such as cracking after steam exposure. Not preferable. As the polycarbonate of the present invention, those having a molecular weight of, for example, a viscosity average molecular weight of 13,000 to 50,000 can be used. When this value is outside the above range, the effect of the present invention is hardly obtained.

The polycarbonate of the present invention is preferably produced by a transesterification reaction. In the present invention, for the raw materials used in the transesterification method,
There is no particular limitation, and various types used for production by a normal transesterification method can be used. For example, in a transesterification reaction, a dihydroxy compound as the component (A) and a carbonic acid diester as the component (B),
(A) component dihydroxy compound diester and (B) component carbonic acid diester, (A) component dihydroxy compound dicarbonate ester and (B) component carbonic acid diester, dihydroxy compound dicarbonate ester (self-condensation), dihydroxy Examples include monocarbonic acid ester (self-transesterification) of the compound. Among these, a dihydroxy compound as the component (A) and a carbonic acid diester as the component (B) are preferably used. The dihydroxy compound as the component (A) is preferably an aromatic dihydroxy compound,
Especially the general formula (III)

[0013]

Embedded image The compound represented by is preferably mentioned. In the general formula (III), R ¹ , R ² , R ³ , R ⁴ , m and n have the same meanings as in the general formula (I).

Examples of the aromatic dihydroxy compound represented by the above general formula (III) include bis (4-hydroxyphenyl) methane; bis (3-methyl-4-hydroxyphenyl) methane; bis (3-chloro-4). -Hydroxyphenyl) methane; bis (3,5-dibromo-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (2-t-butyl-4)
-Hydroxy-3-methylphenyl) ethane; 1-phenyl-1,1-bis (3-fluoro-4-hydroxy-
3-methylphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A);
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane; 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (2-t-butyl-) 4-Hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (3-bromo-4-hydroxyphenyl) propane;
2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-)
4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane;
2,2-bis (4-hydroxyphenyl) octane;
2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; 1,1-bis (4-hydroxy-t-butylphenyl) propane; 2, 2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4
-Hydroxy-3,5-dimethylphenyl) propane;
2,2-bis (4-hydroxy-3-chlorophenyl)
Propane; 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; 2,2-
Bis (3-bromo-4-hydroxy-5-chlorophenyl) propane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2- Bis (3-methyl-4
-Hydroxyphenyl) butane; 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane;
1,1-bis (2-t-butyl-4-hydroxy-5-
Methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) isobutane; 1,1-bis (2-t-amyl-4-hydroxy-)
5-methylphenyl) butane; 2,2-bis (3,5-
Dichloro-4-hydroxyphenyl) butane; 2,2-
Bis (3,5-dibromo-4-hydroxyphenyl) butane; 4,4-bis (4-hydroxyphenyl) heptane; 1,1-bis (2-t-butyl-4-hydroxy-)
5-methylphenyl) heptane; 2,2-bis (4-hydroxyphenyl) octane; bis (hydroxyaryl) such as 1,1- (4-hydroxyphenyl) ethane
Examples include alkanes.

In the production method of the present invention, as the dihydroxy compound as the component (A), an aromatic dihydroxy compound in which m and n are both 0 in the general formula (III) is preferably used, and R ³ Those in which R ⁴ and R ⁴ are both methyl groups are also preferably used, and particularly 2,2
It is preferred to use -bis (4-hydroxyphenyl) propane (bisphenol A). The above compounds may be used alone or in combination of two or more. on the other hand,
In the present invention, there are various carbonic acid diesters used as the component (B). For example, it is at least one compound selected from a diaryl carbonate compound, a dialkyl carbonate compound or an alkylaryl carbonate compound. The diaryl carbonate compound used as one of the components (B) has the general formula (IV)

[0016]

[Chemical 6]

(Wherein Ar ¹ and Ar ² each represent an aryl group, and they may be the same or different from each other), or the general formula (V)

[0018]

[Chemical 7]

(In the formula, Ar ³ and Ar ⁴ each represent an aryl group, which may be the same or different, and D ¹ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound. Is a compound represented by. The dialkyl carbonate compound has the general formula (VI)

[0020]

Embedded image

(In the formula, R ⁵ and R ⁶ each have 1 carbon atom.
~ 6 alkyl group or C4-7 cycloalkyl group, which may be the same or different from each other. ) Or a compound represented by the general formula (VII)

[0022]

[Chemical 9]

(In the formula, each of R ⁷ and R ⁸ has 1 carbon atom.
Indicates 6 alkyl group or a cycloalkyl group having a carbon number of 4-7 and may be the same with or different from each other, a hydroxyl group D ² is from the aromatic dihydroxy compound 2
The residues except for the above are shown. ) Is a compound represented by. The alkyl aryl carbonate compound has the general formula (VIII)

[0024]

[Chemical 10]

(Wherein Ar ⁵ represents an aryl group, R ⁹ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms), or a general formula (IX)

[0026]

[Chemical 11]

(Wherein Ar ⁶ is an aryl group, R ¹⁰ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, and D ³ is the above aromatic dihydroxy compound from which two hydroxyl groups have been removed. The compound represents a residue.).
Here, examples of the carbonic acid diaryl compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and bisphenol A bisphenyl carbonate.

Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate,
Examples thereof include dibutyl carbonate, dicyclohexyl carbonate and bisphenol A bismethyl carbonate. Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. In the present invention, as the carbonic acid diester of the component (B), one kind or two or more kinds of the above compounds are appropriately selected and used, and among these, diphenyl carbonate is preferably used.

Next, as raw materials other than the dihydroxy compound and the carbonic acid diester used in the present invention,
These include: That is, examples of diesters of dihydroxy compounds include diacetic acid ester of bisphenol A, dipropionic acid ester of bisphenol A, dibutyric acid ester of bisphenol A, and dibenzoic acid ester of bisphenol A. Examples of dicarbonic acid esters of dihydroxy compounds include bisphenol carbonic acid ester of bisphenol A, bisethyl carbonic acid ester of bisphenol A, and bisphenyl carbonic acid ester of bisphenol A. Examples of monocarbonic acid esters of dihydroxy compounds include bisphenol A monomethyl carbonic acid ester, bisphenol A monoethyl carbonic acid ester, bisphenol A monopropyl carbonic acid ester, and bisphenol A monophenyl carbonic acid ester.

Examples of the long chain alkyl alcohol used in the production method of the present invention include compounds represented by the following general formula (X). R ¹¹ —OH (X) Here, R ¹¹ has 8 to 30 carbon atoms, preferably 12 to 2 carbon atoms.
Hydrocarbons of No. 4 can be either straight-chain or branched. If the number of carbon atoms of the above hydrocarbon is less than 8, the effect of improving the fluidity is not recognized, and if it exceeds 30, the reactivity is poor and it is difficult to introduce it at the terminal, which is not preferable. In the present invention, examples of the long-chain alkyl alcohol include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol,
Nonadecyl alcohol, eicosyl alcohol, ceryl alcohol, melysyl alcohol, etc. can be used.

The amount of the long-chain alkyl alcohol added is
5 to 95 mol% of all terminal groups of the obtained polycarbonate
May be an amount such that is a group represented by the general formula (II).
It is preferably 10 mol%, more preferably 0.5 to 7 mol%. If the above-mentioned addition amount is less than 0.1 mol%, the effect of improving fluidity is not recognized, and if it exceeds 10 mol%,
It is difficult to control the molecular weight within a desired range. In the production method of the present invention, the reaction rate of the dihydroxy compound and the carbonic acid diester is 50% or more, preferably 60 to
When the value in the range of 95% is reached, the long chain alcohol is melt mixed. When the long-chain alcohol is melt-mixed before the reaction rate reaches 50%, a large amount of low molecular weight components are produced, which is not preferable. In the present invention, the reaction rate means the amount of phenol by-produced (g) as a theoretical amount [(mol number of dihydroxy compound) x 2 x (molecular weight of phenol)].
Divide by and multiply by 100.

In the production method of the present invention, a terminal terminator may be used in combination if necessary. Examples of the terminal terminator include on-n-butylphenol; m-n-butylphenol; pn-butylphenol; o-isobutylphenol; m-isobutylphenol; p-isobutylphenol; ot-butylphenol; mt −
Butylphenol; pt-butylphenol; on
-Pentylphenol; mn-pentylphenol;
p-n-pentylphenol; o-n-hexylphenol; m-n-hexylphenol; p-n-hexylphenol; o-cyclohexylphenol; m-cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m- Phenylphenol; p-phenylphenol; on-nonylphenol; mn-nonylphenol; pn-nonylphenol; o-cumylphenol; m-cumylphenol;
p-cumylphenol; o-naphthylphenol; m-
Naphthylphenol; p-Naphthylphenol; 2,6
-Di-t-butylphenol; 2,5-di-t-butylphenol; 2,4-di-t-butylphenol; 3,
5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; formula

[0033]

[Chemical 12] Or a compound represented by

[0034]

[Chemical 13]

Monohydric phenols such as chroman derivatives represented by Also, the formula

[0036]

Embedded image

Compounds represented by the following can also be used. Furthermore, in the present invention, if necessary, phloroglucin; trimellitic acid; 1,1,1-tris (4-hydroxyphenyl) ethane; 1- [α-methyl-α- (4 ′
-Hydroxyphenyl) ethyl] -4- [α ', α'-
Bis (4 "-hydroxyphenyl) ethyl] benzene;
α, α ', α "-tris (4-hydroxyphenyl)-
1,3,5-triisopropylbenzene; isatin bis (o-cresol) and the like can also be used as a branching agent. Further, in the present invention, a known catalyst such as an inorganic basic compound or an organic basic compound can be used in order to accelerate the transesterification reaction, if necessary. Here, as the inorganic basic compound, for example, simple substance of alkali metal or alkaline earth metal, oxide, hydroxide, amide compound, alcoholate, phenolate, or Zn
Basic metal oxides such as O, PbO and Sb ₂ O ₃ , organic titanium compounds, soluble manganese compounds, Ca, Mg,
Examples thereof include acetate salts such as Zn, Pb, Sn, Mn, Cd, and Co.

On the other hand, examples of the organic basic compound include aliphatic tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine and dimethylbenzylamine, and triphenylamine. Aromatic tertiary amine compounds, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2
-Hydroxypyridine, 4-hydroxypyridine, 2-
Nitrogen-containing compounds such as methoxypyridine, 4-methoxypyridine, imidazole, 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-mercaptoimidazole, aminoquinoline and diazabicyclooctane (DABCO). Heterocyclic compounds, further, ammonium hydroxides having an alkyl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, aryl groups, araryl groups, etc., tetramethylammonium Borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetramethylammo Basic salts such as um tetraphenylborate, other 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (MTB
D); 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and other basic compounds.

Among these compounds, trihexylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide,
Dimethylaminopyridine is preferably used. In addition to the above compounds, boron compounds such as boric acid, trimethyl borate, triethyl borate, tributyl borate, triheptyl borate, triphenyl borate, and trinaphthyl borate can be used as the transesterification catalyst.

[0040] In the present invention, the catalyst may be used also in combination of two or more kinds used alone also the amount used, relative to the dihydroxy compound 1 mole of the starting material, usually 1 × 10 ^- It is selected in the range of ² to 1 × 10 ^-8 mol. If the amount used is less than 1 × 10 ⁻⁸ mol, the catalytic effect may not be sufficiently exerted, and if it exceeds 1 × 10 ⁻² mol, the physical properties of the obtained polycarbonate, particularly heat resistance and hydrolysis resistance, may deteriorate. In addition, it is not preferable because it increases the cost. From the viewpoints of catalytic effect, physical properties of the obtained polycarbonate, and economical efficiency, the preferable amount of the catalyst used is 1 × 1 with respect to 1 mol of the dihydroxy compound.
It is in the range of 0 ⁻³ to 1 × 10 ⁻⁷ mol.

The procedure and conditions of the manufacturing method of the present invention will be specifically described below. First, in order to efficiently react the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B), the carbonic acid diester is 0.9 to 1.5 times, preferably 0.95 times the mol of the dihydroxy compound. ~ 1.2
The transesterification reaction is carried out at a ratio of 5 times mol, more preferably 1.0 to 1.2 times mol. In carrying out the transesterification reaction according to the production method of the present invention, the reaction temperature is not particularly limited and is usually selected in the range of 100 to 350 ° C. The temperature of this transesterification reaction is 1
If it is less than 00 ° C, the reaction rate becomes slow, while if it exceeds 350 ° C, side reactions may occur, or the produced polycarbonate may be colored, which is not preferable. From the viewpoints of reaction rate, suppression of side reactions, quality of polycarbonate and the like, the preferable reaction temperature is in the range of 180 to 330 ° C., and particularly 180 to 30 depending on the progress of the reaction.
A method of raising the temperature to 0 ° C. is preferable.

The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. This is not limited as long as it is set so that the reaction is efficiently performed. Usually, 1 to 50 atm at the beginning of the reaction
In many cases, the atmospheric pressure (normal pressure) up to (760 to 38,000 torr) or the pressurized state is kept, and in the latter stage of the reaction, the reduced pressure state, preferably finally to 0.01 to 10 torr. Further, the reaction time may be such that it reaches the target molecular weight, and is usually about 0.2 to 9 hours. And
The above-mentioned transesterification reaction is usually carried out in the absence of an inert solvent, but if necessary, it may be carried out in the presence of an inert solvent in an amount of 1 to 150% by weight of the obtained polycarbonate. Here, examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene, tricyclo (5,2,10) decane, cyclooctane, cyclodecane, and the like. Examples include cycloalkane. Further, if necessary, it may be carried out in an inert gas atmosphere, where
Examples of the inert gas include various gases such as gases such as argon, carbon dioxide, nitrous oxide and nitrogen, chlorofluorohydrocarbons, alkanes such as ethane and propane, alkenes such as ethylene and propylene.

Further, in the present invention, an antioxidant may be added to the reaction system, if necessary. As the antioxidant, a phosphorus-based antioxidant is preferable, and examples thereof include trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, distearyl. Trialkyl phosphites such as pentaerythyl diphosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite;
Triaryl phosphites such as triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite; 2 -Monoalkyl diaryl phosphites such as ethylhexyl diphenyl phosphite; trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl)
Trialkyl phosphates such as phosphates and tris (2,3-dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate,
Triaryl phosphates such as 2-ethylphenyl diphenyl phosphate and the like can be mentioned.

In the present invention, as the reaction proceeds, phenols corresponding to the carbonic acid diester used,
Alcohols or their esters and inert solvent are desorbed from the reactor. These desorbed substances can be separated, purified and recycled for use, and it is preferable to have a facility for removing them. Further, the present invention can be carried out by either a batch system or a continuous system. In the case of continuous production, it is preferable to use at least two reactors and set the above reaction conditions. The structure of the reactor used in the present invention is not particularly limited, but it is sufficient that the reactor has a normal stirring function. However, since the viscosity increases in the latter stage of the reaction, it is preferable to have a high-viscosity stirring function. Further, the shape of the reaction device is not limited to the tank type, and may be an extruder type reactor or the like.

The polycarbonate obtained as described above may be granulated as it is, or may be molded by using an extruder or the like. Further, the polycarbonate obtained by the present invention can be used by blending well-known additives such as a plasticizer, a pigment, a lubricant, a release agent, a stabilizer and an inorganic filler. Further, the obtained polycarbonate can be blended with a polymer such as polyolefin, polystyrene, polyester, polysulfonate, polyamide and polyphenylene ether. In particular, it is effective when used in combination with polyphenylene ether, polyether nitrile, terminal-modified polysiloxane compound, modified polypropylene, modified polystyrene or the like having an OH group, COOH group, NH ₂ group or the like at the end.

[0046]

The present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the examples below. Examples 1 to 3 In a Ni steel autoclave equipped with a stirrer and having an internal volume of 1.4 liters, 228 g (1.00 mol) of bisphenol A, 225 g (1.07 mol) of diphenyl carbonate, and 0.23 g (2 .5 x 10
^-3 mol), tetrabutylphosphonium hydroxide 2.9
mg (1 × 10 ⁻⁵ mol) was charged, and the inside of the reactor was replaced with nitrogen. This mixture was heated to 180 ° C. to melt bisphenol A and diphenyl carbonate, stirred for 30 minutes, then heated to 210 ° C. and gradually vacuumed to 100 m.
After raising the pressure to mHg, the produced phenol was distilled off. When the distillation of phenol stopped, the weight of phenol distilled was 126 g (reaction rate 65%). Then
After melting and charging the alcohol shown in Table 1, 240
℃, while further distilling phenol 10mmHg
And After that, the temperature is set to 270 ° C and the vacuum degree is set to 0.5 m.
When the reaction was terminated by gradually raising it to mHg for 1 hour, a viscous and transparent condensate remained in the autoclave.

With respect to the substance obtained as described above,
The following evaluation was performed. The results are shown in Table 1. (1) Viscosity average molecular weight (Mv): The intrinsic viscosity [η] of a methylene chloride solution at 20 ° C. was measured and calculated by the formula [η] = 1.23 × 10 ⁻⁵ Mv ^0.83 . (2) Flowability (flow value): temperature of 280 ° C., 160 k
The amount of resin flowing out from a nozzle of 1 mmφ × 10 mm was measured under a pressure of g / cm ² . (3) Acetone-soluble component: A component that has been subjected to Soxhlet extraction using acetone as a solvent. That is, 15 g of the sample polycarbonate that was crushed and passed through a 100-mesh wire net was used as cylindrical filter paper No. 84 (28 x 100 mm)
The mixture was extracted with 300 ml of acetone by refluxing once every 3 to 4 minutes (20 ml / times) for 8 hours. Then, the residue after evaporating 300 ml of acetone was weighed and used as the acetone-soluble component. (4) Thermal stability (ΔYI): An 8 wt% methylene chloride solution of polycarbonate was placed in a quartz cell having a height of 57 mm, and the initial YI (yellow index) was measured using a color meter SM-3 manufactured by Suga Test Instruments Co., Ltd. . Separately
After heat-treating the polycarbonate at 340 ° C. for 30 minutes under a nitrogen stream, the YI after the treatment was measured in the same manner as above. The value obtained by subtracting the initial YI value from the YI value after the above treatment was set as ΔYI. (5) Steam resistance: 280 polycarbonate resin
After press-molding at 5 ° C. to 5 × 5 cm and a thickness of 3.2 cm, and then exposing to steam in a sterilizer at 121 ° C. for 48 hours, it was stored in water.
The number of cracks per 5 × 5 cm plate was measured as follows. Universal projector (OLYMPUS UP
-350), a magnified projection photograph (10 times) was taken using a monochromatic filter, and then 2 by an image analyzer (Stanley Electric Co., Ltd. image analysis system V2.0).
The image was read by a scanner set to 5 cm × 20 cm, and the image was binarized by a discriminant analysis method. The number of particles of 10 pixels (1 pixel = 0.3 mm) or more was counted, and the number obtained by multiplying this measured value by 5 was taken as the number of cracks. (6) Measurement of terminal fractions: Using ¹ H-NMR, determine the mole fractions of the phenoxy group, hydroxyl group and alkyl group.

Example 4 A polycarbonate was produced and evaluated in the same manner as in Example 1 except that the alcohol was charged at a reaction rate of 85% after the temperature was raised to 240 ° C. . The results are shown in Table 1.

Comparative Examples 1 and 2 Polycarbonates were produced and evaluated in the same manner as in Example 1 except that alcohol was added at the same time as bisphenol A and diphenyl carbonate. The results are shown in Table 1.

[0050]

[Table 1] * 1: Regarding the amount of alcohol added, the upper part represents g and the lower part represents the number of moles. * 2: The time of addition is indicated by the reaction rate at the time of addition. Here, the reaction rate was 100 times, by dividing the amount of phenol distilled by 2 mol (194 g) of the amount of phenol distilled when 1 mol of bisphenol A reacted 100%.

[0051]

[Table 2]

[0052]

EFFECT OF THE INVENTION By having a main chain composed of a specific repeating unit and a specific end group, and keeping the acetone-soluble content below a certain value, excellent heat stability and water resistance originally possessed by polycarbonate can be maintained. In addition, a polycarbonate having excellent fluidity can be obtained.

Claims (6)

[Claims] 1. Repeating unit (I): (In the formula, R ¹ and R ² each represent a halogen atom or an alkyl group having 1 to 8 carbon atoms, and m and n each represent 0
Indicates an integer of ˜4. R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ), And 5 to 95 mol% of all terminal groups have the general formula (II) (In the formula, R ¹ , R ² , R ³ , R ⁴ , m and n have the same meanings as those in the above general formula (I), and R represents an alkyl group having 8 to 30 carbon atoms.) A polycarbonate which is a group represented by the formula (3) and has an acetone-soluble content of 3 mol% or less. 2. The polycarbonate according to claim 1, wherein each of R ³ and R ^{4 in the} general formula (I) and the general formula (II) is a methyl group. 3. The general formula (I) and the general formula (II) each have m and n of 0, respectively.
Or the polycarbonate according to 2. 4. When a polycarbonate is produced by a transesterification reaction using a dihydroxy compound and a carbonic acid diester, a long-chain alkyl alcohol is melted when the reaction rate between the dihydroxy compound and the carbonic acid diester reaches a value of 50% or more. A method for producing a polycarbonate, which comprises mixing and polycondensing. 5. The method according to claim 4, wherein the long-chain alkyl of the long-chain alkyl alcohol has 8 to 30 carbon atoms. 6. The dihydroxy compound is 2,2-bis (4-
It is hydroxyphenyl) propane, The manufacturing method of Claim 4 or 5 characterized by the above-mentioned.