JP3099913B2 - Production method of polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst selected from an electron-donating amine compound and a catalyst selected from an alkali metal compound or an alkaline earth metal compound and a catalyst selected from a phosphorus compound. The present invention relates to a method for producing a polycarbonate, which comprises melt-polycondensing a divalent hydroxy compound and a carbonic acid diester by a transesterification method.

[0002]

BACKGROUND OF THE INVENTION The high molecular weight polycarbonates of the present invention are general purpose engineering thermoplastics having a wide variety of uses, particularly for injection molding or as a glass sheet in place of window glass.

In the transesterification reaction, a transesterification catalyst is added to dihydric phenol and carbonic acid diester,
A prepolymer is synthesized while distilling phenol under heating and reduced pressure, and finally heated at 290 ° C. or higher under high vacuum to distill phenol to obtain a high molecular weight polycarbonate (US Pat. No. 4,345,062). ) However, unlike other engineering plastics, high molecular weight polycarbonate has a very high melt viscosity, so it requires a high temperature of 290 ° C or higher as a reaction condition, and a high vacuum is required to distill phenol having a high boiling point. (1 to 1
Since 0 ^-2 Torr) is required, it is known that industrialization is difficult also from the viewpoint of equipment, and that it has an undesirable effect on the hue and physical properties of the polycarbonate produced.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have made a catalyst selected from an electron-donating amine compound with a divalent hydroxy compound and a carbonic acid diester as compounds forming a carbonate bond, and an alkali metal compound or an alkaline earth metal compound. It has been found that polycondensation in the presence of a catalyst selected from the group consisting of and a phosphorus compound results in a high-molecular-weight polycarbonate having no color without using toxic phosgene.

[0005] In particular, the phosphorus compound used here is a very effective compound in that it not only contributes as a transesterification catalyst but also greatly contributes to hue improvement.

The present invention relates to the following inventions 1) to 4). 1) A transesterification method of a divalent hydroxy compound and a carbonic acid diester in the presence of a catalyst selected from an electron-donating amine compound, a catalyst selected from an alkali metal compound or an alkaline earth metal compound, and a catalyst selected from a phosphorus compound A method for producing a polycarbonate, characterized in that the polycondensation is performed by melt polycondensation. 2) A method for producing a polycarbonate, wherein the phosphorus compound according to 1) comprises a combination of at least two or three or more compounds selected from the compounds represented by the following chemical formulas 1, 2, 3, 4, and 5. 3) 2
The method for producing a polycarbonate according to 1) or 2), wherein the polyvalent hydroxy compound is a compound represented by the following chemical formula (6):
4) The process for producing a copolymerized polycarbonate according to 1) or 2), wherein two or more selected from the divalent hydroxy compounds described in 3) are used.

Representative examples of the electron donating amine compound which can be used in the present invention include 4-dimethylaminopyridine,
-Diethylaminopyridine, 4-pyrrolidinopyridine,
4-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-methoxyimidazole, 1-methylimidazole, aminoquinoline, 4-methylimidazole, diazabicyclooctane (DABCO) And the like.

Representative examples of alkali metal compounds and alkaline earth metal compounds include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydrogen carbonate, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, lithium carbonate, and potassium carbonate. , Sodium acetate, lithium acetate, potassium acetate, sodium stearate, lithium stearate, potassium stearate, sodium borohydride, lithium borohydride, potassium borohydride, sodium benzoate, lithium benzoate, potassium benzoate, water Barium oxide, calcium hydroxide, magnesium hydroxide, barium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, barium carbonate, calcium carbonate, magnesium carbonate, barium acetate, calcium acetate, magnesium acetate , Barium stearate, calcium stearate, magnesium stearate and the like.

In the case of phosphorus compounds, tetrakis (2,4-ditertbutylphenyl) -4,4'-biphenylene-di-phosphonite is a typical example of Chemical formula 1, and octadecyl-3- ( 3,5'-di t
tert-butyl-4-hydroxyphenyl) propionate. It is also preferable to use a compound represented by Chemical Formula 3, Chemical Formula 4, or Chemical Formula 5.

[0010] Typical examples of the carbonic acid diester include:
Diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate,
Dicyclohexyl carbonate and the like are used. Of these, diphenyl carbonate is particularly preferred.

The following compounds are typical examples of the divalent hydroxy compound. As bisphenols classified into Chemical Formula 6, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) -4-methylpentane, 2,2-bis- (4
-Hydroxyphenyl) octane, 4,4'-dihydroxy-2,2,2-triphenylethane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane and the like.

As a bisphenol classified in Chemical formula 7,
2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxy-3-
Isopropylphenyl) propane, 2,2-bis- (4
-Hydroxy-3-sec. Butylphenyl) propane, 2-bis- (4-hydroxy-3-tert.butylphenyl) propane, and the like.

As a bisphenol classified in Chemical formula 8,
1,1'-bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 1,1'-bis- (4-hydroxyphenyl) -m-diisopropylbenzene and the like are mentioned.

As a bisphenol classified in Chemical formula 9,
1,1'-bis- (4-hydroxyphenyl) cyclohexane and the like can be mentioned. Furthermore, it is also possible to produce a copolymerized polycarbonate in which two or three or more divalent hydroxy compounds selected from the chemical formulas 6, 7, 8, and 9 are combined.

The process of the present invention uses a catalyst selected from an electron-donating amine compound and a catalyst selected from an alkali metal compound or an alkaline earth metal compound and a catalyst selected from a phosphorus compound, such as bisphenol A. It is carried out by melt polycondensation of a divalent hydroxy compound with a carbonic acid diester.

The temperature at which this reaction proceeds is from 100 ° C. to about 30 ° C.
The range is up to 0 ° C. Preferably 130 ° C to 280 ° C
Range. If the temperature is lower than 130 ° C., the reaction rate becomes slow, and if it exceeds 280 ° C., side reactions tend to occur.

The electron-donating amine compound used as a catalyst requires from 10 ^-1 mol to 10 ^-5 mol, preferably from 10 ^-2 mol to 1 mol of the divalent hydroxy compound present in the reaction system. 10 ^-4 mol. When the amount is less than 10 ^-5 mol, the catalytic action is small, and the polymerization rate of the polycarbonate is slow. When the amount is 10 ^-1 mol or more, the rate of remaining in the produced polycarbonate becomes high, so that the physical properties of the polycarbonate are deteriorated.

Further, the alkali metal compound and the alkaline earth metal compound used as the combined catalyst require from 10 ⁻² mol to 10 ⁻⁶ mol, preferably from 10 ⁻² mol to 1 mol of the divalent hydroxy compound present in the reaction system. Is from 10 ⁻³ mol to 10 ⁻⁵ mol. If the amount is less than 10 ^-6 mol, the catalytic action is small, and the polymerization rate of the polycarbonate is reduced.
^If it is more than ^-2 mol, the rate of remaining in the produced polycarbonate becomes high, so that the physical properties of the polycarbonate are deteriorated.

Further, the phosphorus compound used as the combined catalyst requires 10 ^-4 mol to 10 ^-6 mol, preferably 10 ^-3 mol to 1 mol of the divalent hydroxy compound present in the reaction system. 10 ^-5 mol.

The required amount of the carbonic acid diester is equivalent to the molar amount of the divalent hydroxy compound present in the reaction system.
Generally, in order to produce a high molecular weight polycarbonate,
One mole of the carbonate compound and one mole of the divalent hydroxy compound must react. When diphenyl carbonate is used, 2 moles of phenol are formed by the reaction. These two moles of phenol are distilled out of the reaction system.

However, the carbonic acid diester used is 1.01-1.
It is desirably used in an amount of 5 mol, preferably 1.015 to 1.05 mol.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0023]

Example 1 2,2-bis (4-hydroxyphenyl)
22.8 g (0.1 mol) of propane, 21.9 g (0.1025 mol) of diphenyl carbonate, 0.024 g (2 × 10 ⁻⁴ mol) of 4-dimethylaminopyridine, 0.098 mg (1 × 10 ⁻ ) of potassium acetate ⁶ mol) and 0.01 g (1 × 10 ⁻⁵ mol) of the phosphorus compound represented by Chemical Formula ⁵ are placed in a Hastelloy separable flask under nitrogen at 180 ° C.
Melt and stir well, raise the temperature while gradually reducing the pressure,
Finally, the temperature was adjusted to 0.1 Torr and 270 ° C., and the formed phenol was distilled off to obtain a colorless and transparent polycarbonate. The viscosity average molecular weight (M
When v) was measured, Mv = 29,000. As a method of measuring the viscosity average molecular weight, the intrinsic viscosity [η] of the methylene chloride solution at 20 ° C. was measured using an Ubbelohde viscometer, and the viscosity average molecular weight (Mv) was calculated using the following equation. [Η] = 1.11 × 10 ⁻⁴ (Mv) ^0.82 The glass transition temperature was 150 ° C.

[0024]

Example 2 0.016 g of 2-methylimidazole (2 × 10 ^-3 mol) instead of 4-dimethylaminopyridine and 0.01 g of calcium carbonate instead of potassium acetate under exactly the same conditions as in Example 1 1 × 10 ⁻⁴ mol), and 0.005 g (8 × 10 ⁻⁶ mol) of the phosphorus compound represented by Chemical Formula 4 in place of the phosphorus compound represented by Chemical Formula 5, was used in the same manner as in Example 1. The condensation reaction was performed to obtain a colorless and transparent polycarbonate. The viscosity average molecular weight was 28,000 and the glass transition temperature was 149 ° C.

[0025]

Example 3 2,2-bis (4-hydroxyphenyl)
11.4 g (0.05 mol) of propane, 17.0 g (0.05 mol) of 2,2-bis (4-hydroxy-3-tertbutylphenyl) propane, 22.5 g (0.105 mol) of diphenyl carbonate 0.0024 g (2 × 10 ⁻⁵ mol) of 4-dimethylaminopyridine, 0.098 mg (1 × 10 ⁻⁶ mol) of potassium acetate, and 0.01 g (1 × 10 ⁻⁵ mol) of the phosphorus compound represented by the formula ( ⁵ ) Was melted under nitrogen, and then subjected to a polycondensation reaction in the same manner as in Example 1 with stirring to obtain a colorless and transparent polycarbonate. The viscosity average molecular weight is 25,500 and the glass transition temperature is 12
8 ° C.

[0026]

Comparative Example 1 2,2-bis (4-hydroxyphenyl)
22.8 g (0.1 mol) of propane, 22.0 g (0.1025 mol) of diphenyl carbonate and iron chloride (3 mol.
In a flask and melt at 180 ° C. under nitrogen,
When the mixture was stirred well and reacted in the same manner as in Example 1, the obtained polycarbonate had a viscosity average molecular weight of 2,
000 and red.

[0027]

By using a catalyst selected from an electron-donating amine compound, a catalyst selected from an alkali metal compound or an alkaline earth metal compound, and a catalyst selected from a phosphorus compound, substantially no phosgene is used without using toxic phosgene. As a result, a colorless and transparent polycarbonate having a high molecular weight and containing no chlorine was obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-54223 (JP, A) JP-A-3-149221 (JP, A) JP-A-3-255125 (JP, A) JP-A-3-255 26722 (JP, A) JP-A-1-272263 (JP, A) Mikio Matsugane, Shogo Tahara, Shuji Kato, "Plastic Materials Course 5 Polycarbonate Resin", Nikkan Kogyo Shimbun, September 30, 1969, p. 63 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (4)

(57) [Claims] 1. 10 moles per mole of a divalent hydroxy compound
^-5 to 10 ^-1 mol of a catalyst selected from an electron-donating amine compound and 10 ^{-6 to} 1 mol of a divalent hydroxy compound.
A catalyst selected from 10 to 10 ^-2 moles of an alkali metal compound or an alkaline earth metal compound and a divalent hydroxy compound
Production of a polycarbonate characterized by subjecting a divalent hydroxy compound and a carbonic acid diester to melt polycondensation by a transesterification method in the presence of a catalyst selected from 10 ^-6 to 10 ^-4 mol of a phosphorus compound per 1 mol of a product. Law. 2. The method according to claim 1, wherein the phosphorus compound is
A method for producing a polycarbonate, comprising a combination of at least two or three or more compounds selected from compounds represented by 2,3,4,5. Embedded image Embedded image Embedded image Embedded image Embedded image (R ₁ represents a hydrocarbon group having 1 to 30 carbon atoms.) 3. The method according to claim 1, wherein the divalent hydroxy compound is
The method for producing a polycarbonate according to claim 1, wherein Embedded image Embedded image Embedded image Embedded image (R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or C 1-8
Represents an alkyl group or a phenyl group containing a straight chain or a branch, X represents a halogen atom, n = 0 to 4, and m =
1 to 4. ) 4. The method according to claim 3, wherein two or more kinds selected from the divalent hydroxy compounds according to claim 3 are used.
The method for producing the copolymerized polycarbonate described in the above.