JP3099912B2 - Production method of polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polycarbonate, and more particularly to a method for producing a polycarbonate capable of obtaining a colorless, transparent and high-molecular-weight polycarbonate.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate is a versatile engineering thermoplastic that has a wide range of uses, particularly for injection molding or as a glass sheet instead of window glass.

Hitherto, interfacial polycondensation, transesterification and the like have been applied to the production of these polycarbonates.
The interfacial polycondensation method is generally effective for the production of polycarbonate, but has disadvantages such as the use of toxic phosgene and the generation of chloride ions in the polycarbonate.

In order to solve these drawbacks, a method for producing a polycarbonate by interfacial polycondensation reaction with a special dihydric phenol using liquid trichloromethyl chloroformate which is a phosgene dimer instead of toxic phosgene. Is disclosed in JP-A-63-182336.

However, there is only description of 9,9-bis (4-hydroxyphenyl) fluorenes as a special dihydric phenol. In addition, triphosgene is used in place of toxic phosgene to give 2,2-bis (4
A method for obtaining polycarbonate from (-hydroxyphenyl) propane is described in Angew. Chem. (Angevante.
Hemy) 99.922 (1987), German Patent DE3
Although described in the specification of 440141, a reaction mechanism for generating phosgene has also been proposed.

[0006] In the transesterification reaction, a transesterification catalyst is added to diphenyl carbonate and an aromatic dihydroxy compound, and a prepolymer is synthesized while distilling off phenol under heating and reduced pressure.
The phenol is distilled off by heating at a temperature of not less than ℃ 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 is also required to distill phenol having a high boiling point. Since a high vacuum (10 ^-2 Torr) is required, industrialization is difficult from the viewpoint of equipment, and it is known that there are problems in terms of hue and physical properties.

However, various studies have been made on the transesterification method since it is possible to carry out the reaction by melt polycondensation and is an industrially economical method.
In particular, the influence of the material of the reactor is suggested from the viewpoint of product coloring. As described in JP-A-55-1422025, when a stainless steel reactor is used, the obtained polycarbonate is colored. In many cases, it is difficult to obtain a polymer having a high molecular weight, which suggests that it is difficult to produce a product satisfying both physical properties and hue. In addition, special catalysts have been found by studying various catalysts, but they have not always been satisfactory.
Further, although different from the starting material of the present invention, U.S. Pat. No. 4,383,092 also discloses a description relating to reactor materials.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on high molecular weight and resin coloring, which are one of the problems of the transesterification method conventionally used in the production of polycarbonate. As a result, the present inventors have found that a colorless, transparent, high-molecular-weight polycarbonate can be obtained by using a special material particularly for the liquid contact portion, and have completed the present invention.

That is, the present invention provides a method for producing a polycarbonate by melt-polycondensing a divalent hydroxy compound and a bisaryl carbonate in the presence of a transesterification catalyst by a transesterification method. quantitative relation the total content of Ni及beauty a l 60% or more (however, the content of Ni of 0% and Al
It is intended to provide a method for producing a polycarbonate for obtaining a high-molecular-weight, colorless and transparent resin by using a material comprising (excluding 0%) .

A more detailed description will be given. In the present invention, the extent the total content is 60% or more of Ni及beauty A l as the material of the portion in contact with the material or polycarbonate reaction of the reactor, a high molecular weight and colorless transparent polycarbonate is obtained. Other components include F
e, Pb, Zn, Ti, V and the like, and the case where a trace amount is present is also included in the present invention. The other components are not limited to these. Ni
及beauty or inhibit molecular weight and the total content of A l is less than 60%, coloration of the resulting resin is promoted.

Representative examples of the transesterification catalyst which can be used in the present invention include (a) lithium borohydride, sodium borohydride, potassium borohydride, rubidium borohydride as a catalyst similar to a metal-containing catalyst. ,
Cesium borohydride, beryllium borohydride, magnesium borohydride, calcium borohydride, strontium borohydride, barium borohydride, aluminum borohydride, titanium borohydride, tin borohydride, germanium borohydride, Lithium tetraphenoxy, sodium tetraphenoxy, potassium tetraphenoxy, tetraphenoxyrubidium, tetraphenoxycesium, sodium thiosulfate, beryllium oxide, magnesium oxide, tin oxide (tetravalent), dibutyltin oxide, beryllium hydroxide, magnesium hydroxide, hydroxide Germanium, beryllium acetate, magnesium acetate, tin acetate (tetravalent), germanium acetate, lithium carbonate, sodium carbonate, potassium carbonate, beryllium carbonate, magnesium carbonate Um, tin carbonate (tetravalent), carbonate germanium, tin nitrate (tetravalent), germanium nitrate, antimony trioxide, bismuth trimethyl carboxylate.

(B) As a catalyst similar to the electron donating amine compound, N, N-dimethyl-4-aminopyridine,
4-diethylaminopyridine, 4-aminopyridine, 2
-Aminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 4-hydroxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-mercaptoimidazole, aminoquinoline, imidazole, 2-methylimidazole,
4-methylimidazole, diazabicyclooctane (D
ABCO) and the like.

Also, (c) the above-mentioned electron-donating amine compounds such as carbonic acid, acetic acid, formic acid, nitric acid, nitrous acid, oxalic acid, boronic acid, hydrofluoric acid and the like. (D) Examples of the catalyst similar to the electron-donating phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tri-o-dimethoxyphenylphosphine, and tri-p. -Tolyl phosphine, tri-o-tolyl phosphine, tributyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, tri-o-tolyl phosphite and the like.

Further, (e) a catalyst similar to the borane complex includes a complex of borane and the following compound, namely, ammonia, dimethylamine, trimethylamine, triethylamine, t-butylamine, dimethylaniline, pyridine, dimethylaminopyridine, morpholine, Complexes such as piperazine, pyrrole, tetrahydrofuran, dimethylsulfide, tri-n-butylphosphine, triphenylphosphine, and triphenylphosphite are exemplified. Particularly preferred transesterification catalysts include an electron donating amine compound or a combination of an electron donating amine compound and an alkali metal compound or an alkaline earth metal compound.

The divalent hydroxy compound used in the present invention includes, for example, compounds represented by the following formulas (1) to (4). Specifically, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) butane, 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, 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, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-tert-butylphenyl) propane, 1,1′-bis- ( 4-hydroxyphenyl) -p
-Diisopropylbenzene, 1,1'-bis- (4-hydroxyphenyl) -m-diisopropylbenzene,
1,1-bis- (4-hydroxyphenyl) cyclohexane and the like can be mentioned. Furthermore, it is also possible to produce a copolymerized polycarbonate by combining these two or three or more divalent hydroxy compounds.

As the bisaryl carbonate, diphenyl carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2,4,6-trichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate, bis (o- Nitrophenyl) carbonate,
Examples include ditolyl carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and the like. Preferably, it is diphenyl carbonate.

The production method of the present invention comprises subjecting a divalent hydroxy compound such as bisphenol A to a melt polycondensation reaction with a bisaryl carbonate such as bisphenyl carbonate using at least one of the above-mentioned transesterification catalysts. Will be implemented.

The temperature at which this reaction proceeds is from 100 ° C. to about 30 ° C.
The range is up to 0 ° C. The reaction temperature is preferably in the range of 130C to 280C. Reaction temperature 130 ° C
If the temperature is less than 280 ° C., the reaction rate becomes slow, and if it exceeds 280 ° C., side reactions tend to occur. The at least one compound selected as a catalyst requires 10 ^-1 mol to 10 ^-5 mol, preferably 10 ^-2 mol to 10 ^-5 mol, based on the divalent hydroxy compound present in the reaction system. ^-4 mol. When the amount of the catalyst is less than 10 ^-5 mol, the catalytic action is small and the polymerization rate of the polycarbonate is slowed. When the amount of the catalyst is 10 ^-1 mol or more, the rate of remaining in the produced polycarbonate becomes high, so Causes the deterioration of the physical properties.

The required amount of the bisaryl carbonate is equimolar to the amount of the divalent hydroxy compound present in the reaction system. In general, one mole of a carbonate compound and one mole of a divalent hydroxy compound must react to produce a high molecular weight polycarbonate. However, industrially, bisaryl carbonate is conventionally treated with an excess of 1.00 to 1.10 mol of bisaryl carbonate with respect to the hydroxy compound, which is included in the conditions of the present invention.

In the present invention, a bonding material using the above substance as a surface material or a plated material is also included.

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

[0022]

Embodiment 1 Dura nickel 301 (Ni 95%, A
l 4.4%, Ti 0.6%)
-Bis (4-hydroxyphenyl) propane 22.8 g
(0.1 mol), 2-methylimidazole 0.0164
g (2 × 10 ^-4 mol) and bisphenyl carbonate 2
1.9 g (0.1023 mol) was added, and 1
After stirring at 80 ° C. for 1 hour, the temperature was increased while gradually reducing the pressure,
Finally, a polycondensation reaction was performed at 0.1 Torr and 270 ° C. for 2 hours, and the generated phenol was distilled off to obtain a colorless and transparent polycarbonate. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, it was Mv = 31,000. Further, the hue was A ₃₈₀ -A ₅₈₀ = 0.08.

Here, the method for measuring the viscosity average molecular weight is as follows.
The intrinsic viscosity [η] of the methylene chloride solution at 0 ° 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 hue was evaluated using a 10% methylene chloride solution of polycarbonate using a UV measurement device at 380 nm and 580 n.
The difference in absorbance in the wavelength region of m was measured and displayed, and the larger the value, the more the color was colored.

[0024]

Embodiment 2 Dura nickel 301 (Ni 95%, A
l 4.4%, Ti 0.6%)
0.0061 g of 4-dimethylaminopyridine (5 ×) as a transesterification catalyst instead of 2-methylimidazole
10 ^-5 mol) and 0.00049 g of potassium acetate (5 ×
^Except for using 10 ^-6 mol), the same reaction as in Example 1 was carried out to obtain a polycarbonate. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, Mv = 34.0
00. The hue is A ₃₈₀ −A ₅₈₀ = 0.0
It was 8.

[0025]

Example 3 Using a reaction vessel made of Pyrex glass,
Ni powder 70ppm, Al powder 30p based on charged amount
pm was added, and the reaction was carried out in the same formulation as in Example 2.
When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, it was Mv = 33,000. Further, the hue was A ₃₈₀ -A ₅₈₀ = 0.06.

[0026]

Embodiment 4 The addition amounts of Ni powder and Al powder were 50 p each.
The reaction was carried out in the same manner as in Example 3 except that pm and 50 ppm were used. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, it was Mv = 32,000. Further, the hue was A ₃₈₀ −A ₅₈₀ = 0.10.

[0027]

Embodiment 5 Ni powder 35 ppm, Al powder 35 pp
The reaction was carried out in the same manner as in Example 3 by adding 15 ppm of m, Fe powder and 15 ppm of Mo powder. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, M
v = 29,000. The hue is A ₃₈₀ -A
₅₈₀ = 0.115.

[0028]

Example 6 Same as Example 5 except that 0.0061 g (5 × 10 ⁻⁵ mol) of 4-dimethylaminopyridine and 0.00049 g (5 × 10 ⁻⁶ mol) of potassium acetate were used in combination as a transesterification catalyst. Did the trick. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, M
v = 35,000. The hue is A ₃₈₀ -A
₅₈₀ = 0.07.

[0029]

Comparative Example 1 Stainless steel (SUS316: Fe 67
%, Cr 18%, Ni 12%, Mo 25%, C
0.06%), and the reaction was carried out in the same manner as in Example 2 to obtain a polycarbonate. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, M
v = 21,000. The hue is A ₃₈₀ -A
₅₈₀ = 0.38.

[0030]

Comparative Example 2 Stainless steel (SUS304: Fe 74)
%, Cr 18%, Ni 8%, C 0.06%), and the reaction was carried out in the same manner as in Example 2 to obtain a polycarbonate. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, it was Mv = 20,000. The hue was A ₃₈₀ −A ₅₈₀ = 0.40.

[0031]

Comparative Example 3 Using a reaction vessel made of carbon steel (SS-41), a reaction was carried out in the same manner as in Example 2 to obtain a polycarbonate. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, it was Mv = 17,000. The hue was A ₃₈₀ −A ₅₈₀ = 0.50.

[0032]

Comparative Example 4 In Example 3, Ni powder 20 ppm, A
1 powder 20ppm, Fe powder 45ppm, Ti 15p
The reaction was performed in the same manner except that pm was added. When the viscosity average molecular weight (Mv) of the obtained polycarbonate was measured, it was Mv = 19,400. The hue is A
It was ₃₈₀ -A ₅₈₀ = 0.401.

[0033]

According to the present invention, a colorless and transparent polycarbonate having a high molecular weight and no color can be obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-72327 (JP, A) JP-A-2-153927 (JP, A) JP-A-3-26722 (JP, A) JP-A-4- 88017 (JP, A) JP-A-5-125169 (JP, A) JP-A-5-125172 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64 / 42

Claims (4)

(57) [Claims] In a method for producing a polycarbonate by melt-polycondensation of a divalent hydroxy compound and a bisaryl carbonate in the presence of a transesterification catalyst by a transesterification method, a quantitative relation of a composition constituted as a material of a reactor is provided. There total content of Ni及beauty a l 60% or more (only
Except that the Ni content is 0% and the Al content is 0%.
C) performing a transesterification reaction using a material comprising: 2. A method according to claim 1, wherein the material in contact with the reactant comprises the composition according to claim 1. 3. The process according to claim 1, wherein the transesterification catalyst comprises an electron-donating amine compound or a combination of an electron-donating amine compound and an alkali metal compound or an alkaline earth metal compound. 4. The method according to claim 1, wherein the divalent hydroxy compound is
Or the compound represented by formula (4). Embedded image Embedded image Embedded image Embedded image (R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or a phenyl group, X represents a halogen atom, n = 0
4, m = 1 to 4. )