JP3112838B2 - Method for producing polycarbonate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polycarbonate composition, and more particularly to a method for efficiently producing a polycarbonate composition in which additives are uniformly dispersed and which has excellent heat stability.

[0002]

2. Description of the Related Art Polycarbonate is known as an engineering plastic having excellent heat resistance, impact resistance, transparency, etc., and is widely used in many fields. In recent years, as a polycarbonate production method, research and development of a production method by a melt transesterification method have been actively conducted in order to substitute a phosgene method having problems in toxicity and environmental safety.

[0003] It is known that in the production of polycarbonate by the melt transesterification method, since the polycarbonate is in a molten state at the time of completion of the polymerization reaction, it can be granulated as it is (Plastic Materials Course 5 Polycarbonate resin, P62-P67, Nikkan Kogyo Shimbun, published in 1969) does not know about a specific method for adding an additive such as a heat stabilizer or a method for supplying polycarbonate to an extruder.

For example, JP-A-5-310906 and JP-B-5-46843 disclose a method of adding a phosphorus-based heat stabilizer at the time of melt polymerization or at the end stage.
No. 26 proposes a method of adding a heat stabilizer during a molten state after polymerization. However, the former method has a problem in that the stabilizer is decomposed or modified during the polymerization, so that coloring occurs or the polymerization rate is reduced. Further, in the latter method, since the heat stabilizer is added after the polymerization, there is no problem as in the former, but it is only described that the polycarbonate and the heat stabilizer are kneaded by a twin-screw extruder. No specific method is described.

On the other hand, the stabilizers used in polycarbonate, especially heat stabilizers, are used in a very small amount of 0.0001 to 0.1 part by weight with respect to 100 parts by weight of polycarbonate, so that they are uniformly melted. Difficult to mix. In the case of the phosgene method, there was no problem because mixing and melt-extrusion can be performed by a usual method after adding a heat stabilizer dissolved in methylene chloride to a powdery or slurry-like polycarbonate containing a methylene chloride solvent. .

However, in the melt transesterification method,
Since the molten polycarbonate can be directly granulated, the method of supplying the heat stabilizer and the uniform mixing have been problems. Specifically, the heat stabilizer is a powder or granular heat stabilizer at room temperature,
In the case of direct addition from the second supply port of the twin-screw extruder, the amount of supply per unit time itself was too small, so that the quantitativeness of the quantitative feeder was limited, and the amount of addition was large. When the polycarbonate composition obtained as a result is used as a molding material, there is a problem that coloring is likely to occur. Further, when the supply amount of the heat stabilizer per unit time is small, there is a problem that there is no usable feeder. In addition, when a solid heat stabilizer is heated and melted at room temperature and supplied to an extruder or the like by a pump, there is a problem in that the heat stabilizer is thermally deteriorated and the obtained polycarbonate is colored. Also, when a heat stabilizer or additive which is liquid at room temperature is supplied by a pump, if the amount of addition is small, dispersion of the addition may occur, and coloring may occur when the obtained polycarbonate composition is used as a molding material. There is a problem that is easy to occur. When the additive is diluted and increased with a solvent such as methylene chloride and added through a liquid injection port, the dispersibility of the additive is improved, but the solvent is contained in the obtained polycarbonate composition by several tens to several thousand ppm. Since it remains, there is a problem that coloring tends to occur when used as a molding material. Therefore, there is still no method for efficiently adding a heat stabilizer to a polycarbonate produced by a melt transesterification method and efficiently obtaining a polycarbonate composition having excellent heat stability with little coloring when used as a molding material. Is the current situation.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a molten polycarbonate produced by a melt transesterification method,
It is an object of the present invention to provide a method for efficiently producing a polycarbonate composition having excellent heat stability by uniformly dispersing additives.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a method of adding polycarbonate in a molten state and an additive. As a result, a twin-screw extruder was used as an extruder. By supplying the heat stabilizer to the extruder after diluting it with another polycarbonate,
The present inventors have found the surprising fact that a polycarbonate composition having little coloring and excellent heat stability when used as a molding material can be obtained, and the present invention has been achieved.

That is, the present invention provides: (1) a polycarbonate produced by transesterification from an aromatic dihydroxy compound and a carbonic acid diester,
After being supplied to the first supply port of the extruder in the molten state, at least one of the additives is mixed with another or the same type of polycarbonate and supplied from the second supply port of the extruder,
A method for producing a polycarbonate composition to be mixed with the polycarbonate, wherein the polycarbonate produced by transesterification from the aromatic dihydroxy compound and a carbonic acid diester is a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or an aromatic dihydroxy compound. A polymerization intermediate obtained by reacting a compound and a diaryl carbonate, characterized in that it is a polycarbonate produced by a transesterification method including a step of polymerizing while dropping along a guide from a perforated plate in a molten state. (2) Polycarbonate produced by transesterification from an aromatic dihydroxy compound and a carbonic acid diester in a molten state, and pressurizing and supplying the polycarbonate to a first supply port of an extruder. The feature described in (1) above (3) The polycarbonate according to the above (1), wherein the form of the polycarbonate supplied from the second supply port is a granular form and / or a powder form having a minor axis of 1 mm and a major axis of 3 mm. (4) The polycarbonate composition according to the above (1), wherein the other polycarbonate supplied from the second supply port is a granular and / or powdered polycarbonate produced by a phosgene method. (5) The polycarbonate supplied from the second supply port is:
(1) The method for producing a polycarbonate composition according to (1), wherein the polycarbonate has a weight average molecular weight in a range of 5,000 to (weight average molecular weight of the polycarbonate supplied from the first supply port) x 1.1. , Is provided.

[0010]

Hereinafter, the present invention will be described in detail.

In the present invention, the aromatic dihydroxy compound is a compound represented by HO-Ar-OH (wherein, Ar represents a divalent aromatic group).

The aromatic group Ar is preferably, for example, -A
a divalent aromatic group represented by r ¹ -Y-Ar ^2- (wherein, Ar ¹ and Ar ² each independently have 5 to 5 carbon atoms)
Represents a divalent carbocyclic or heterocyclic aromatic group having 70, and Y represents a divalent alkane group having 1 to 30 carbon atoms. ).

In the divalent aromatic groups Ar ¹ and Ar ² , 1
One or more hydrogen atoms do not adversely affect the reaction, other substituents, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, It may be substituted by a cyano group, an ester group, an amide group, a nitro group or the like.

Preferred specific examples of the heterocyclic aromatic group include an aromatic group having one or more ring-forming nitrogen, oxygen or sulfur atoms.

The divalent aromatic groups Ar ¹ and Ar ² are, for example,
Represents a group such as a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted pyridylene; The substituent here is as described above.

The divalent alkane group Y is, for example, an organic group represented by the following chemical formula.

[0018]

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(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms,
A cycloalkyl group having 5 to 10 ring carbon atoms, a carbocyclic aromatic group having 5 to 10 ring carbon atoms, and a carbocyclic aralkyl group having 6 to 10 carbon atoms. k is 3 to 1
Represents an integer of 1, R ⁵ and R ⁶ are individually selected for each X, independently of each other, represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents carbon. R ¹ , R ² ,
In R ³ , R ⁴ , R ⁵ , and R ⁶ , other substituents such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms are provided as long as one or more hydrogen atoms do not adversely affect the reaction. 1
It may be substituted with 0 alkoxy group, phenyl group, phenoxy group, vinyl group, cyano group, ester group, amide group, nitro group and the like. Examples of such a divalent aromatic group Ar include those represented by the following chemical formula.

[0020]

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(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cyclo group having 5 to 10 ring carbon atoms) An alkyl group or a phenyl group, m and n
Is an integer of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and n is 2 to 4
In this case, each R ⁸ may be the same or different. In addition, the divalent aromatic group Ar is represented by -Ar ¹ -Z-Ar ^2-
May be indicated.

(Wherein Ar ¹ and Ar ² are as described above, and Z
Is a single bond or -O -, - CO -, - S -, - SO 2 -,
-SO -, - COO -, - CON (R 1) - represents a divalent group, such as. Here, R ¹ is as described above. Examples of such a divalent aromatic group Ar include those represented by the following chemical formula.

[0023]

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(In the formula, R ⁷ , R ⁸ , m and n are as described above.) The aromatic dihydroxy compound used in the present invention may be a single kind or two or more kinds. A typical example of the aromatic dihydroxy compound is bisphenol A. Further, it is preferable that the content of the chlorine atom and the alkali metal or alkaline earth metal is small, and it is preferable that these aromatic dihydroxy compounds are not substantially contained if possible.

The carbonic acid diester used in the present invention is represented by the following chemical formula.

[0026]

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(Wherein, Ar ³ and Ar ⁴ each represent a monovalent aromatic group.) Ar ³ and Ar ⁴ each represent a monovalent carbocyclic or heterocyclic aromatic group. ³ , In Ar ⁴ , one or more hydrogen atoms do not adversely affect the reaction, for example, another substituent such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group. , A phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group and the like. Ar
³ and Ar ⁴ may be the same or different.

Representative examples of the monovalent aromatic groups Ar ³ and Ar ⁴ include a phenyl group, a naphthyl group, a biphenyl group and a pyridyl group. These may be substituted with one or more substituents described above.

Preferred examples of Ar ³ and Ar ⁴ include the following chemical formulas.

[0030]

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Representative examples of the carbonic diester include substituted or unsubstituted diphenyl carbonates represented by the following chemical formula.

[0032]

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(Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
An alkoxy group having 10; a cycloalkyl group having 5 to 10 ring carbon atoms; or a phenyl group;
When p is 2 or more, each R ⁹ may be different, and when q is 2 or more,
Each R ¹⁰ may be different. Among these diphenyl carbonates, unsubstituted diphenyl carbonate, ditolyl carbonate, di-t
Symmetric diaryl carbonates such as lower alkyl-substituted diphenyl carbonates such as -butylphenyl carbonate are preferred, but diphenyl carbonate, which is the diaryl carbonate having the simplest structure, is particularly preferred.

These carbonic acid diesters may be used alone or in combination of two or more. In addition, it is preferable that these carbonic acid diesters have a small content of a chlorine atom and an alkali metal or an alkaline earth metal, and it is preferable that they are substantially not contained if possible.

The ratio of the aromatic dihydroxy compound and the carbonic acid diester (the charge ratio) depends on the kind of the aromatic dihydroxy compound and the carbonic acid diester, the polymerization temperature and other polymerization conditions, and the molecular weight and terminal ratio of the polycarbonate to be obtained. The diaryl carbonate is usually 0.9 to 2.5 mol, preferably 0.95 to 2.0 mol, more preferably 0.98 to 1.5 mol, based on 1 mol of the aromatic dihydroxy compound. Used in proportion.

In the present invention, an aromatic polyhydric hydroxy compound for introducing a branched structure may be used in combination with a hydroxy terminal and a terminal derived from a carbonic acid diester within a range not to impair the object of the present invention. Aromatic monohydroxy compounds or other carbonic acid diesters may be used in combination to convert the compound or to control the molecular weight.

The molecular weight and terminal groups of the polycarbonate of the present invention are not particularly limited. Generally, a weight average molecular weight of 10
In the range of from 00 to 300,000, preferably 5000
-100,000, particularly preferably 1200.
It is in the range of 0-80000.

In the present invention, the transesterification means that the compound is subjected to polycondensation by transesterification in a molten state while heating under reduced pressure and / or under an inert gas flow in the presence or absence of a catalyst. This refers to a method, and there is no limitation on the polymerization method, apparatus, and the like. For example, a stirred tank reactor, a thin-film reactor, a centrifugal thin-film evaporation reactor, a surface-renewal twin-screw kneading reactor, a twin-screw horizontal stirring reactor, a wet-wall reactor,
It can be easily produced by using a perforated plate reactor which polymerizes while freely falling, a perforated plate reactor with a wire which polymerizes while being dropped along a wire, or the like, alone or in combination. Among these, surface renewal type twin screw kneading reactor, twin screw horizontal stirring reactor, wet wall type reactor,
A perforated-plate reactor which polymerizes while freely falling and a perforated-plate reactor with a wire which polymerizes while being dropped along a wire are preferably used. A perforated plate reactor with a wire, which is polymerized while being dropped, is preferable since polycarbonate with less coloring can be obtained. The temperature of the transesterification reaction is generally selected in the range of 50 to 350 ° C, preferably 100 to 300 ° C, and is not particularly limited. In general, at a temperature higher than the above range, the obtained polycarbonate tends to be greatly colored and have poor thermal stability. If the temperature is lower than the above range, the polymerization reaction is slow and not practical. The reaction pressure varies depending on the molecular weight of the polycarbonate during melt polymerization. When the number average molecular weight is 1,000 or less, the range of 50 mmHg to normal pressure is generally used, and the number average molecular weight is 1,000 to 200.
In the range of 0, the range of 3 mmHg to 80 mmHg is used, and in the range of the number average molecular weight of 2,000 or more, 10 mmHg or less, particularly 5 mmHg or less is used.

The additives used in the production method of the present invention are not particularly limited as long as they are those used for polycarbonate. Generally, heat stabilizers, antioxidants, weathering agents, release agents, lubricants, antistatic agents, plasticizers, pigments, dyes, fillers, reinforcing agents, flame retardants, polymers such as other resins and rubbers, and the like. Can be Examples of preferred heat stabilizers include phosphorus stabilizers, phenol stabilizers, sulfur stabilizers, epoxy stabilizers, hindered amine stabilizers, and the like.

Examples of the phosphorus-based stabilizer include phosphoric acids, phosphites, phosphinates, phosphates, and phosphonates. Specifically, for example, as the phosphoric acids, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphinic acids represented by the following chemical formula,

[0041]

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Examples thereof include phosphonic acids represented by the following chemical formula.

[0043]

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(Wherein R ¹¹ is an alkyl group such as an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a 2-ethylhexyl group, a decyl group, a tridecyl group, a lauryl group, a pentaerythritol group, a stearyl group, a phenyl group, An aryl group such as a naphthyl group, or a tolyl group, a Pt-butylphenyl group, a 2,4-di-t-butylphenyl group,
And alkylaryl groups such as a 2,6-di-t-butylphenyl group, a paranonylphenyl group, and a dinonylphenyl group. ) Specific examples of these include phenylphosphonic acid.

The phosphites include phosphite triester, phosphite diester and phosphite monoester, and are represented by the following chemical formula.

[0046]

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[0047]

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[0048]

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[0049]

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(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ ,
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , and R ²³ may be the same or different in the compound, and may be hydrogen, ethyl, butyl,
Octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group, alkyl group such as stearyl group, phenyl group, aryl group such as naphthyl group, or tolyl group, Pt
- butylphenyl group, 2,4-di -t- butyl phenyl group, 2,6-di -t- butyl phenyl group, p-nonylphenyl group, an alkylaryl group, such as di-nonylphenyl group, R ^17, R ²⁴ represents alkylene, arylene, or arylalkylene. As specific examples of these, for example, in the case of phosphite triester, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris Phenyl phosphite, tetraphenyl dipropylene glycol phosphite, tetra (tridecyl) 4,4′-isopropylidene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl4-methylphenyl) pentaerythritol diphosphite, distearyl, pentaerythritol diphosphite, hydrogenated Bisuf Nord A · pentaerythritol diphosphite polymer, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite. Specific examples of the phosphite diester include diphenyl hydrogen phosphite, bis (nonylphenyl) hydrogen phosphite, bis (2,4-di-t-butylphenyl) hydrogen phosphite, dicresyl hydrogen phosphite, and (bis (p -T-butylphenyl) hydrogen phosphite, bis (p-hexylphenyl) hydrogen phosphite, etc. Examples of the phosphite monoester include phenyl dihydrogen phosphite, nonylphenyl dihydrogen phosphite, and 2,4-diphenyl. -T-butylphenyl dihydrogen phosphite and the like.

The phosphinic esters include phosphinic diesters and phosphinic monoesters, and are represented by the following chemical formula.

[0052]

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[0053]

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(Wherein R ²⁵ represents an alkyl group such as an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a 2-ethylhexyl group, a decyl group, a tridecyl group, a lauryl group, a pentaerythritol group, a stearyl group, a phenyl group, An aryl group such as a naphthyl group, or a tolyl group, a Pt-butylphenyl group, a 2,4-di-t-butylphenyl group,
2,6-di -t- butyl phenyl group, p-nonylphenyl group, an alkylaryl group, such as di-nonylphenyl ^{group, R 26, R 27, R} 28, R 29, R 31, R 32 is the compound May be the same or different, and include hydrogen, an ethyl group,
Butyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group, alkyl group such as stearyl group,
Aryl groups such as phenyl group and naphthyl group, or tolyl group, Pt-butylphenyl group, 2,4-di-t-butylphenyl group, 2,6-di-t-butylphenyl group, paranonylphenyl group , A dinonylphenyl group or the like, and R ³⁰ represents alkylene, arylene, or arylalkylene. ) Specific examples of such compounds include tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphinate.

Examples of the phosphoric esters include phosphoric diesters and phosphoric monoesters, and are represented by the following chemical formula.

[0056]

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[0057]

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[0058]

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[0059]

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(Wherein R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ ,
R ¹⁹ , R ²¹ , R ²³ and R ²⁴ are the same as described above. As specific examples of the phosphoric diester, for example, diphenyl hydrogen phosphate, bis (nonylphenyl) hydrogen phosphate, bis (2,4-di-t-butylphenyl) hydrogen phosphate, dicresyl hydrogen phosphate, (bis (pt -Butylphenyl) hydrogen phosphate, bis (p-hexylphenyl) hydrogen phosphate and the like.
Specific examples of the phosphoric acid monoester include phenyl dihydrogen phosphate, nonylphenyl dihydrogen phosphate, 2,4-di-t-butylphenyl dihydrogen phosphate, and the like.

Examples of the phosphonates include phosphonate monoesters, which are represented by the following chemical formula.

[0062]

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[0063]

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(Wherein R ²⁵ , R ²⁷ , R ²⁹ , R ³⁰ , R ³¹ ,
^R32 is the same as described above. The phenolic stabilizer is represented by the following chemical formula.

[0065]

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(In the formula, R ³³ represents a hydrogen atom, a hydroxyl group, an alkoxyl group or a hydrocarbon residue which may have a substituent, and R ³³ may be the same or different, provided that R ³³
At least one represents a hydrocarbon residue which may have a substituent. Specifically, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-p-anisole, 2,6
-Di-t-butyl-4-ethylphenol, 2,2'-
Methylene bis (6-t-butyl-p-cresol),
2,2′-methylenebis (4-ethyl-6-t-butyl-p-phenol), 4,4′-methylenebis (6-t
-Butyl-p-cresol), 4,4'-butylidenebis (6-t-butyl-m-cresol), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4').
-Hydroxyphenyl) propionate] methane, 4,
4'-thiobis (6-t-butyl-m-cresol),
Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3-
(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-
Hydroxybenzylphosphonate-diethyl ester, calcium bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium and the like.

The sulfur-based stabilizer is represented by the formula: R ³⁶ -SO
Sulfinic acid represented by ₂ -R ^37, wherein: R ³⁶ -SO ₃ R ³⁷
(In both formulas, R ³⁶ is the same as R ^11, and R ³⁷ is the same as R ¹² ).

[0068]

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(In the formula, R ³⁸ and R ^{39 each} represent a C12 to C18 alkyl group.) Specific examples thereof include, for example, benzenesulfinic acid, p-toluenesulfinic acid, benzenesulfonic acid, p-toluene Sulfonic acid, naphthalene sulfonic acid,
And methyl, ethyl, butyl, octyl and phenyl esters of these acids. Also, dilauryl-3,
3'-thiodipropionate, ditridecyl-3,3 '
-Thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol (β-laurylthiopropionate) and the like.

Examples of the epoxy stabilizer include fats and oils such as epoxy soybean oil and epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, bisphenol A diglycidyl ether, and tetrabromobisphenol A diglycidyl. Glycidyl compounds such as ether, diglycidyl phthalate and diglycidyl hexahydrophthalate, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxy-6-methylcyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
2,3-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4- (3,4-
Epoxy-5-methylcyclohexyl) butyl-3,4
-Epoxycyclohexanecarboxylate, 3,4-
Epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate,
Bisepoxycyclohexyl adipate, octadecyl-2,2'-dimethyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2,2'-dimethyl-3,4-epoxycyclohexanecarboxylate,
Cyclohexyl-2-methyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexanecarboxylate, octadecyl-3,4-epoxycyclohexanecarboxylate, 2-ethylhexyl −
3,4-epoxycyclohexanecarboxylate,
4,6-dimethyl-2,3-epoxycyclohexyl-
3,4-epoxycyclohexanecarboxylate, diethyl-4,5-epoxy-cis-1,2-cyclohexanecarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2 -Cyclohexanecarboxylate, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3, -methyl-5-t-butyl-
Epoxycyclohexane compounds such as 1,2-epoxycyclohexane, bisepoxydicyclopentadienyl ether, butadiene diepoxide, tetraphenyleylene epoxide, epoxidized polybutadiene, 4,5-epoxytetrahydrophthalic anhydride, 3- t-butyl-
4,5-epoxytetrahydrophthalic anhydride and the like.

Examples of the hindered amine-based stabilizer include bis (2,2,6,6-tetramethyl-4-biperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-).
4-biperidyl) sebacate, 2- (3,5-di-t-)
Bis (1,2,2,6,6-pentamethyl-4-biperidyl) tetraxy (2,2,6,6-tetramethyl-4-biperidyl) butyl-4-hydroxybenzyl) -2-nbutylmalonate ) 1,2,3,4-butanetetracarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) polopionyloxy}
Ethyl] -4- {3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) polopionyloxy} -2,2,2
6,6-tetramethylpiperidine, 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 and the like.

These heat stabilizers may be used alone or in combination. The amount of addition is not particularly limited, but is generally used in the range of 0.0001 to 0.5 part by weight based on 100 parts by weight of polycarbonate.

In the method for producing the composition of the present invention, the polycarbonate produced by the above-mentioned method is supplied in a molten state to a first supply port of an extruder, and at least one of the additives is mixed with another or similar polycarbonate. Mixing, supplying the mixture from a second supply port of the extruder, and mixing with the polycarbonate.

The extruder used in the production method of the present invention is not particularly limited as long as it has at least the first and second supply ports, and may be a single-screw, twin-screw or multi-screw extruder, or a kneader and an extruder. A kneading extruder or the like connected with a machine can be used. Among them, a co-rotating twin-screw extruder is preferable because of good balance between the dispersibility of the additive and the discharge ability and the self-cleaning property. The length of the extruder is not particularly limited, but the polycarbonate added from the second supply port is in the form of pellets, granules, powder, or the like,
When supplied in a non-molten state, the polycarbonate must be sufficiently long to dissolve, knead and mix. The second supply port may be located on the extruder outlet side of the first supply port, and the positional relationship is not particularly limited.

The method for supplying the polycarbonate obtained by the transesterification method to the first supply port of the extruder in a molten state is not particularly limited. Generally, the extruder is supplied to a first supply port, for example, a hopper port of the extruder using a free fall or a gear pump. Preferably, a method in which the line from the gear pump is directly connected to the first supply port by a flange or the like, and the pressure is supplied to the extruder by the gear pump because the discharge capacity of the extruder increases.

The method of supplying the mixture of the additive and the polycarbonate from the second supply port of the extruder can be a known method, and is not particularly limited. For example, a method of directly supplying the mixture metered by a weight or volume feeder to the second supply port in an unmelted state, or a method of supplying the mixture metered by a weight or volume feeder to the second supply port. Or a method in which the mixture is supplied in an unmelted state via a side feeder, or in a molten state by an extruder connected to the second supply port.

The method of mixing the additive with another or the same type of polycarbonate is not particularly limited. For example, there is a method of uniformly mixing with an Henschel mixer, a super mixer, a turn bull mixer, a ribbon blender or the like. The mixture may be supplied as it is from the second supply port by the above-mentioned method, or may be melt-mixed by another extruder to obtain an additive master batch pellet, and then the second supply by the above-mentioned method. It may be supplied by mouth. Further, when supplied from the second supply port in a non-molten state, the form of the polycarbonate used when mixing with the additive, pellets, granules, powder-like and the like is used, particularly, the short diameter Granular particles and / or powder particles smaller than 1 mm long diameter 3 mm are preferably used. In the present invention, since the supply ratio of the polycarbonate supplied from the second supply port is smaller than that of the polycarbonate supplied from the first supply port, the polycarbonate produced by the phosgene method, which can be easily supplied as a powder, is used. Can also be used.
However, since the polycarbonate powder obtained by the phosgene method contains some chlorine atoms, depending on the supply ratio of the polycarbonate supplied from the second supply port and the polycarbonate supplied from the first supply port, the chlorine powder contains It is preferable to use one having a low content, and it is also preferable to use it after washing with a solvent or the like to reduce the chlorine atom content. The finally obtained polycarbonate composition of the present invention preferably has a chlorine content of 0.5 ppm or less as chloride ions and 1 ppm or less as methylene chloride.

The polycarbonate supplied from the second supply port may be the same as or different from the polycarbonate supplied from the first supply port. The molecular weight is not particularly limited. However, the molecular weight of another polycarbonate supplied from the second supply port is from 5,000 to
(Weight average molecular weight of the polycarbonate supplied from the first supply port) × 1.1 is preferable because the dispersibility of the additive is improved. When the same type of polycarbonate is used, before the polycarbonate obtained by the transesterification method is supplied to the first supply port of the extruder in a molten state, pelletized or powdered polycarbonate is collected in a small amount. And a method in which polycarbonate obtained as a product is fractionated and used.

The mixing ratio of the additive and the polycarbonate supplied from the second supply port and the ratio to the polycarbonate supplied from the first supply port are not particularly limited. The supply amount of the additive is determined by the blending amount with respect to the polycarbonate supplied from the first supply port, and the amount of the polycarbonate supplied from the second supply port may be any amount that can efficiently and uniformly supply the additive. Generally, the amount of the polycarbonate supplied from the second supply port is 1/1000 to the amount of the polycarbonate supplied from the first supply port.
It is at a ratio of 1/20.

The composition obtained by the method of the present invention has excellent heat stability because the additives are uniformly dispersed and does not contain a dispersing solvent or other dispersing agents. It can be suitably used.

[0081]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples.

The evaluation of each item was measured by the following method.

Color: Measured by a CIELAB method at a test piece thickness of 3.2 mm, and the yellowness was indicated by a b ^* value.

Heat resistance: Test piece (ASTM No. 1 dumbbell)
Was placed in a 140 ° C. gear oven for 1000 hours, the color of the test piece was measured, and the difference Δb ^* from the initial value was evaluated.

The amount of chloride ions in the polycarbonate was determined by adding water to the frozen and pulverized polycarbonate, extracting the mixture in boiling water for 10 hours, and measuring the water by an ion chromatography method.

The amount of methylene chloride in the polycarbonate was determined by immersing frozen and pulverized polycarbonate in carbon disulfide and ultrasonically extracting the extract by gas chromatography.

Example 1 A polycarbonate composition was produced from a polycarbonate obtained by melt polymerization by a transesterification method, using an apparatus shown in FIG.

Polycarbonate having a weight average molecular weight of 25,000 obtained by a transesterification method was supplied from a line 1 connected to a melt polymerization vessel, and was supplied to a gear pump 2 at 20 kg / cm 2.
² of boosted pressure, supplied to the first supply port 4 of the co-rotating twin screw extruder 3 at a feed rate of 50 kg / hr. On the other hand, from the second supply port 5, 0.5 parts by weight of tris (2,4-di-t-butylphenyl) phosphite as an additive and the same polycarbonate as the polycarbonate supplied from the supply port 1 with a diameter of 0 0.6 mm long 3 mm pellets
A mixture in which 5 parts by weight and a Henschel mixer were sufficiently mixed in advance was supplied at a rate of 1.0 kg / hr. Melt extrusion was performed while vacuum-venting at the vent port 6, and a polycarbonate composition was obtained via the cooling bath 7 and the strand cutter 8. After the evaluation of the heat resistance of the obtained composition, the test piece had a small Δb ^* color of 8.2 and uniform coloration.

Example 2 Except for using polycarbonate powder (weight average molecular weight 21,000, chlorine ion content 0.7 ppm, methylene chloride content 9 ppm) produced by the phosgene method as the polycarbonate supplied from the supply port 2 Example 1
Was performed in the same manner as described above. The composition obtained had a chloride ion content below the detection limit and a methylene chloride content of 0.1.
ppm, the coloring Δb ^* of the test piece after the heat resistance evaluation was as small as 9.1, and the coloring was uniform.

Comparative Example 1 A polycarbonate composition was produced from a polycarbonate obtained by melt polymerization by a transesterification method using an apparatus shown in FIG.

A polycarbonate having a weight average molecular weight of 25,000 obtained by a transesterification method was supplied from a line 1 connected to a melt polymerization vessel, and 10 kg / cm
² of boosted pressure, supplied to the first supply port 4 of the co-rotating twin screw extruder 3 at a feed rate of 50 kg / hr. On the other hand, the supply port 2 is closed, and a 4% by weight solution of tris (2,4-di-t-butylphenyl) phosphite in methylene chloride as an additive is supplied from the liquid injection port 9 at a rate of 120 ml / hr. A composition was obtained. In the obtained composition, 78 ppm of methylene chloride remained, and the color of the test piece after heat resistance evaluation was uniform, but Δb ^*
Was as large as 17.7.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the polycarbonate supplied from the supply port 2 was not used and only tris (2,4-di-t-butylphenyl) phosphite was supplied at a rate of 5 g / hr. Carried out. However, such a small amount of feeder was not commercially available, so it was manually intermittently supplied. The coloring Δb ^* of the test piece after the heat resistance evaluation of the obtained composition was 2
It was as large as 3.6, and coloring was also observed.

[0093]

According to the present invention, an additive can be uniformly dispersed in a molten polycarbonate produced by a melt transesterification method, and a polycarbonate composition having excellent heat stability can be efficiently produced. be able to.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an embodiment of a method for producing the polycarbonate composition of the present invention.

[Explanation of Signs] 1 Connection line with melt polymerization reactor of transesterification method 2 Gear pump 3 Co-rotating twin screw extruder 4 First supply port 5 Second supply port 6 Vent port 7 Cooling bath 8 Strand cutter 9 Liquid injection Entrance 10 side feeder

Claims (5)

(57) [Claims] 1. After a polycarbonate produced by transesterification from an aromatic dihydroxy compound and a carbonic acid diester is supplied in a molten state to a first supply port of an extruder, at least one of additives is added to another extruder. Or a method of producing a polycarbonate composition mixed with the same kind of polycarbonate and supplied from the second supply port of the extruder, and mixed with the polycarbonate, wherein the aromatic dihydroxy compound and the carbonic acid diester are transesterified. The produced polycarbonate, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate, is dropped along a guide from a perforated plate in a molten state. Manufactured by transesterification including the process of polymerizing A method for producing a polycarbonate composition, characterized by being a polycarbonate. 2. A polycarbonate produced by transesterification from an aromatic dihydroxy compound and a carbonic acid diester is supplied to a first supply port of an extruder by applying a pressure in a molten state. 2. A method for producing the polycarbonate composition according to 1. 3. The method for producing a polycarbonate composition according to claim 1, wherein the form of the polycarbonate supplied from the second supply port is granular and / or powdery having a minor axis of 1 mm and a major axis of 3 mm. 4. The other polycarbonate supplied from the second supply port is granular and / or granular produced by the phosgene method.
The method for producing a polycarbonate composition according to claim 1, wherein the polycarbonate composition is a powdery polycarbonate. 5. The polycarbonate supplied from the second supply port is a polycarbonate having a weight average molecular weight in a range of 5,000 to (weight average molecular weight of the polycarbonate supplied from the first supply port) × 1.1. The method for producing a polycarbonate composition according to claim 1, wherein: