JP3394115B2 - Method for producing polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a polycarbonate.
And a method for producing the same. More specifically, polymerization reaction rate, color
Phase, heat resistance, etc.
I do. [0002] 2. Description of the Related Art Polycarbonate is used for mechanical properties such as impact resistance.
Excellent heat resistance, transparency, etc.
Widely used. Such polycarbonate
The production method of aromatic dihydrogen such as bisphenol
A method for directly reacting a hydroxy compound with phosgene (see
Surface method) or aromatic dihydro such as bisphenol
Xy compounds and diaryl carbonates such as diphenyl carbonate
Transesterification in the molten state with sodium carbonate (melting method)
There are known methods for causing them to do so. [0003] Among such production methods, aromatic dihydro-
Transesterification of xy compounds with diaryl carbonates
Method for producing polycarbonate by reaction
To illustrate, this method uses a metal organic acid as a catalyst.
Salts, inorganic acid salts, oxides, hydroxides, hydrides or
Aromatic dihydroxy under reduced pressure using
The compound and the diaryl carbonate are, for example, finally
Transesterification while heating and melting at 250-330 ° C
It is a method of reacting. [0004] This method has a higher poly-polymethod than the aforementioned interface method.
It has the advantage of being able to produce carbonates at low cost.
However, because the polymer is exposed to high temperatures for a long time,
There was a problem that the phase was not favorable. Color like this
Various catalysts have been proposed to improve the phase.
Inferior to polycarbonate polymerized by surface method, still sufficient
is not. In the melt polymerization method, high temperature and reduced pressure are used in the presence of a catalyst.
Because the reaction is performed, the polymer is easily colored and side reactions occur.
Polycarbonate with Less Coloring Due to Branching Structure
Some catalyst systems for the production of
Kilammonium hydroxy and alkali metal, alkali
Catalyst systems combining earth metals have been proposed. I
However, when an alkali metal compound is used,
Of methyl chloride which is considered to be due to a branched structure in the polymer
Components insoluble in solvents such as ren may be formed. Branch
The generation of insolubles due to the structure becomes more pronounced as the degree of polymerization increases.
Become. [0006] Molding of the obtained polycarbonate
In some cases, the degree of polymerization decreases greatly. In addition, the resin
Exposure to warm atmosphere may cause oxidation reaction and other decomposition
Coloration, insolubilization, formation of foreign matter, molecular weight
There are problems such as price. [0007] Accordingly, the present invention provides
No coloration by the melt polymerization method and the obtained polycarbonate
During molding of Bonate, resin coloration and generation of foreign matter are reduced.
Not to provide a way to produce polycarbonate
Aim. [0008] SUMMARY OF THE INVENTION The present invention is directed to a specific catalyst system.
By performing polymerization in the presence of, almost no coloring,
Moreover, high molecular weight polycarbonate soluble in solvent is produced
It is characterized by being able to. That is, the present invention relates to an aromatic dihydroxy compound.
Melt polycondensation of the compound with the diaryl carbonate
When producing carbonate, (A) basification with nitrogen
Compound (B) an alkali metal compound and / or an alkali
Lithium earth metal compounds and (C) hindered phenol
The reaction is carried out in the presence of a catalyst comprising
This is a method for producing polycarbonate. Aromatic dihydroxylation for use in the present invention
The compound is not particularly limited, but is represented by the following formula (1).
Compounds. [0011] Embedded image In the formula, X is [0013] Embedded image ## EQU1 ## Here, R_Three, R_FourAre the same or different,
Hydrogen atom, halogen atom or hydrocarbon having 1 to 12 carbon atoms
Elementary group. As the hydrocarbon group, a fatty acid having 1 to 12 carbon atoms
Aliphatic hydrocarbon group or aromatic hydrocarbon having 6 to 12 carbon atoms
Preferred are basic groups. Such aliphatic hydrocarbon groups include
A kill group, an alkenyl group, etc., a methyl group, an ethyl group.
And a propyl group. Also aromatic hydrocarbon groups
Is a substituted or unsubstituted phenyl group, naphthyl group
And the like. Halogen atoms include chlorine, bromine,
And urine. R_FiveIs a divalent hydrocarbon group having 4 to 20 carbon atoms
And an aliphatic carbon such as an alkylene group or an alkenylene group.
A hydrogen group, such as a butylene group and a pentylene group;
Is done. Where R₁, R_TwoAre the same or different,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms
is there. As the hydrocarbon group, an aliphatic carbon having 1 to 12 carbon atoms
Examples include a hydride group or an aromatic group having 6 to 12 carbon atoms.
Can be. As the aliphatic hydrocarbon group, an alkyl group, a
Examples thereof include a alkenyl group, and more specifically, a methyl group,
Examples include an ethyl group and a propyl group. Also with aromatic groups
Substituted or unsubstituted phenyl group, naphthyl group, etc.
Is mentioned. Halogen atoms include chlorine, bromine and iodine
Element and the like. In the formula, m and n are the same or different, and 0 or
Represents an integer of 1 to 4. Specifically, the following compounds are listed.
Can be. Bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxyphenyl) butane, 2,2-bi
Bis (4-hydroxyphenyl) octane, bis (4-hi
Droxyphenyl) phenylmethane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 1,1
-Bis (4-hydroxy-t-butylphenyl) propa
2,2-bis (4-hydroxy-3-bromophenyl)
B) bis (hydroxyaryl) alka such as propane
And 1,1-bis (4-hydroxyphenyl) cyclo
Pentane, 1,1-bis (4-hydroxyphenyl) si
Bis (hydroxyaryl) cyclo such as chlorohexane
Alkanes, 4,4'-dihydroxydiphenylate
4,4'-dihydroxy-3,3'-dimethylfe
Dihydroxyaryl ethers such as nyl ether,
4,4'-dihydroxydiphenyl sulfide, 4,
4'-dihydroxy-3,3'-dimethyldiphenyls
Dihydroxydiaryl sulfides such as sulfide,
4,4'-dihydroxydiphenylsulfoxide, 4,
4'-dihydroxy-3,3'-dimethyldiphenyls
Dihydroxydiaryl sulfoxides such as rufoxide
, 4,4'-dihydroxydiphenylsulfone, 4,
4'-dihydroxy-3,3'-dimethyldiphenyls
Dihydroxydiaryl sulfones such as rufone, 9,
Such as 9-bis (4-hydroxyphenyl) fluorene
And dihydroxydiaryls. Of these, in particular, 2,2-bis (4-
Hydroxyphenyl) propane (bisphenol A)
It is preferably used. These aromatic dihydroxy compounds
The objects can be used alone or in combination. Diaryl carbonate has 6 to 2 carbon atoms.
Carbonate having 0 optionally substituted aryl groups
Although there is no particular limitation as long as it is a
Nyl carbonate, ditolyl carbonate, bis (c
(Rolophenyl) carbonate, m-cresyl carbonate
G, dinaphthyl carbonate, bis (diphenyl) car
Bonate and the like can be mentioned. Zia as above
Reel carbonate is 1 mole of aromatic dihydroxy compound
1.0 to 1.30 mol, preferably 1.
Preferably, it is used in an amount of from 01 to 1.20 mol. The catalyst used in the present invention is (A) a nitrogen-containing salt.
Basic compound, (B) an alkali metal compound and / or
Alkaline earth metal compound and (C) hindered pheno
A urea compound. (A) Specific examples of the nitrogen-containing basic compound and
As a result, tetramethylammonium hydroxide (Me
_FourNOH), tetraethylammonium hydroxide
(Et _FourNOH), tetrabutylammonium hydroxy
Sid (Bu_FourNOH), trimethylbenzylammonium
M-hydroxide (phenyl-CH_Two(Me)_ThreeNOH)
Having an alkyl, aryl, araryl group, etc.
Ammonium hydroxides, trimethylamine,
Liethylamine, dimethylbenzylamine, triphenyl
Tertiary amines such as_TwoNH (where R is methyl
Alkyl such as ethyl, ethyl, phenyl, toluyl, etc.
An aryl group, etc.), RN
H_Two(Wherein R is as defined above)
, 2-methylimidazole, 2-phenylimidazo
And other imidazoles, tetramethylammonium
Acetate (Me_FourNOCOCH_ThreeAmmonium such as
Mucarboxylates or tetramethylammonium
Umboro hydride (Me _FourNBH_Four), Tetrabuty
Luammonium tetraphenylborate (Bu_FourNBP
h_Four), Tetramethylammonium tetraphenylbore
(Me_FourNBPh _Four))
Can be. Of these, ammonium hydroxide
Are preferred, and tetramethylammonium hydro
Oxide (Me_FourNOH) is particularly preferred. These compounds
The substances may be used alone or in combination of two or more. (B) Alkali metal compounds, alkaline earths
As metal compounds, these hydroxides, bicarbonates,
Carbonates, acetates, borohydrides, stearates, ammonium salts
There are salts of benzoate and bisphenol. As a specific example of the alkali metal compound,
Is sodium hydroxide, potassium hydroxide, lithium hydroxide
, Sodium bicarbonate, potassium bicarbonate, bicarbonate
Lithium, sodium carbonate, potassium carbonate, lithium carbonate
System, sodium acetate, potassium acetate, lithium acetate,
Sodium stearate, potassium stearate, steer
Lithium phosphate, sodium benzoate, potassium benzoate
System, lithium benzoate, disodium hydrogen phosphate, phosphorus
Dipotassium hydrogen oxyphosphate, dilithium hydrogen phosphate, bispheno
Disodium salt, dipotassium salt, dilithium
Salt, phenol sodium salt, potassium salt, lithium
Salts and the like can be mentioned. Specific examples of alkaline earth metal compounds
Examples include calcium hydroxide, barium hydroxide, hydroxyl
Magnesium iodide, strontium hydroxide, hydrogen bicarbonate
Cium, barium bicarbonate, magnesium bicarbonate, charcoal
Strontium hydrogen oxy, calcium carbonate, barium carbonate
, Magnesium carbonate, strontium carbonate, calcium acetate
Cium, barium acetate, magnesium acetate, acetate acetate
Nitium, calcium stearate, bali stearate
, Magnesium stearate, stearic acid
And nthium. These compounds
One type or two or more types may be used in combination. (C) As a hindered phenol compound
Has one or both of the ortho positions of the phenolic OH group
Compound having a phenol structure substituted with an alkyl group
It is. Specific examples of hindered phenol compounds
2,6-di-tert-butyl-4-methylphenol
, N-octadecyl-3- (4-hydroxy-3,5
-Di-t-butylphenyl) propionate, triethyl
Lenglycol-bis [3- (3-tert-butyl-5-me
Tyl-4-hydroxyphenyl) propionate],
2,2'-methylenebis (4-methyl-6-t-butyl
Phenol), 4,4'-butylidenebis (3-methyl
-6-t-butylphenol), tetrakis [methylene
-3- (3,5-Di-tert-butyl-4-hydroxyphen)
Nyl) propionate] methane, 1,1,3-tris
(2-Methyl-4-hydroxy-5-t-butylphenyi
Le) butane, distearyl (4-hydroxy-3-methyl)
Ru-5-t-butyl) benzylmalonate, 4-hydro
Xydimethyl-2,6-di-t-butylphenol
These may be used alone or in combination of two or more.
May be. The amount of these catalysts used is aromatic dihydrogen.
For 1 mole of the droxy compound, (A) 10 parts of nitrogen-containing basic compound^-6-10^-1Mole (B) Alkali metal compound and / or alkaline earth
10 metal compounds^-8-10^-FourMole (C) 10 hindered phenol compounds^-6-10^-2Mo
Le Is preferred. More preferably, aromatic dihydroxylation
Per mole of compound (A) 10 parts of nitrogen-containing basic compound^-Five-10^-3Mole (B) Alkali metal compound and / or alkaline earth
10 metal compounds^-7-10^-FiveMole (C) 10 hindered phenol compounds^-Five-10^-3Mo
Le Is preferred. Above this range, colored or branched components
Is easy to produce, and below this range, the effect of the catalyst is low.
In addition, a sufficient reaction rate cannot be obtained, and the physical properties are likely to deteriorate. In the present invention, the method of charging the catalyst is
It does not matter whether it is liquid or liquid, but it is preferably a solution or a suspension.
It is liquid. The concentration of the solution or suspension is liquid
Any concentration that can be handled in a good condition, preferably 30 weight
%, More preferably 20% by weight or less. The solution
Or the concentration of oxygen dissolved in the suspension is 100ppm or less
And more preferably 50 ppm or less, more preferably
More preferably, it is 10 ppm or less. This range
If it exceeds, coloring or branching components may occur due to the effect of dissolved oxygen.
Easy to generate. Further, in the present invention, before polymerization is started,
During fusion, at least once in the molten state after polymerization
It is also preferable to add various stabilizers. As the stabilizer
The sulfur-containing acidic compound and / or the acid compound
Derivatives, phenolic stabilizers, thioe
-Tel stabilizer, phosphorus stabilizer, hindered amine based stabilizer
Stabilizer, epoxy compound, salicylic acid UV absorber,
Nzotriazole UV absorbers
You. As described above, the combination in the above-mentioned amount is used.
The reacted catalyst allows the polycondensation reaction to proceed at a sufficient
Of low molecular weight polycarbonate with high polymerization activity
Is preferred. In the presence of such a catalyst, the aromatic dihydro
Polycondensation reaction between xy compound and diaryl carbonate
Under the same conditions as conventionally known polycondensation reaction conditions.
It can be carried out. Specifically, the first-stage reaction is carried out at 80 to 25.
0 ° C, preferably 100 to 230 ° C, more preferably
At a temperature of 120-190 ° C, 0-5 hours, preferably 0
~ 4 hours, more preferably 0 ~ 3 hours, under reduced pressure, fragrance
Reaction between an aromatic dihydroxy compound and a diaryl carbonate
Respond. Then, while increasing the degree of vacuum in the reaction system,
To increase the aromatic dihydroxy compound and the diaryl car
Reaction with Bonate, finally 5mmHg or less,
Preferably under a reduced pressure of 1 mmHg or less, 240 to 320
Aromatic dihydroxy compound and diaryl carbonate at ℃
And a polycondensation reaction with The above-mentioned polycondensation reaction is carried out continuously.
Or a batch process. In addition, the above reaction
The reactor used for the reaction is a tank type
It may be of a type or a tower type. The reaction product obtained as described above
Polycarbonate, which is usually measured at 20 ° C.
Viscosity (methylene chloride solvent (weight ratio 40/6)
0)) is 0.1 to 1.0, preferably 0.2 to 0.8
is there. In the present invention, the poly
Normal carbonates do not impair the purpose of the present invention.
Heat stability, UV absorber, release agent, colorant, antistatic
Agent, lubricant, antifogging agent, natural oil, synthetic oil, wax, organic
A filler, an inorganic filler, and the like may be added. [0040] According to the present invention, the polymer color tone is good and the
The reaction is suppressed, and even when the degree of polymerization is increased, it is also caused by the branching reaction
Polycarbonate with low generation of insoluble matter and foreign matter
Can be built. Branching reaction and other side reactions during molding
Is suppressed, and burns, coloring, insolubilization, and foreign matter generation in the equipment are suppressed.
Formation can be suppressed at a low level. [0041] The present invention will be described below with reference to examples. Book
In the present invention, physical properties were measured according to the following methods. (I) Intrinsic viscosity [η]: Ubero in methylene chloride at 20 ° C
It was measured with a te viscometer. (Ii) Filterability, black foreign matter: Polymer in SUS316 test tube
Was obtained by treating at −290 ° C. for 20 hours in a nitrogen stream.
The polymer was ground. 5 g of the polymer is dissolved in 10 methylene chloride.
The mixture was added to 0 ml, ultrasonically washed and dissolved. Poly obtained
0.5 kg of the mer solution with a 1 micron Millipore filter
/ Cm^TwoUnder pressure. The filterability is “good”: filtration in less than 15 minutes,
"Somewhat bad" ... filtration in 15-30 minutes, "poor" ... filtration
The evaluation was made in three stages, with the time exceeding 30 minutes. On the filter
Black foreign substances are "small" ... less than 10, "medium" ... 10-2
0, “many”... More than 20 were evaluated in three stages. (Iii) Hue: (A) L / b: cylinder temperature of an injection molded plate having a thickness of 3 mm
300 ° C injection pressure 100kg / cm^TwoAt a mold temperature of 90 ° C
After molding, the X, Y and Z values were measured using Colora
nd Color Difference Meter
  L / b was measured by a transmission method using ND-1001DP. (B) Haze: NDH manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at -200. [Examples 1 and 2, Comparative Examples 1 to 4]
No. A 228 parts, diphenyl carbonate 220 parts
The catalyst of the type and amount shown in Table 1 and Table 2 was stirred with a stirrer and distilled.
The reactor was equipped with a pressure vessel and a decompression device.
After that, it was melted at 140 ° C. After stirring for 30 minutes,
Was heated to 180 ° C., and the pressure was gradually reduced to 3 at 100 mmHg.
Phenol reacting for 0 minutes was distilled off. Further, the pressure was gradually reduced while increasing the temperature to 200 ° C.
Reacted while distilling phenol at 50 mmHg for 30 minutes
I let you. Further, gradually at 220 ° C. to 30 mmHg
The temperature was increased and the pressure was reduced.
0 mmHg, 1 mmHg at 260 ° C, 1 mm at 270 ° C
Repeat the heating and depressurization in the same procedure as above until the pressure drops below Hg
The reaction was continued. Finally, polymerization was carried out at the same temperature and pressure for 2 hours,
A carbonate resin was produced. The physical properties of these polycarbonate resins are shown in the following table.
It is described in the following table. According to the present invention, the polymerization rate was high,
Polycarbonate generates less insoluble contaminants and quickly
It could be filtered. On the other hand, according to Comparative Example 1, the polymerization activity was low,
Insufficient, and according to Comparative Examples 2 and 3
Many gel-like foreign substances were found on the filter in Comparative Example 4.
According to the report, the reaction speed at low temperature is slow and the hue is deteriorated.
Was. According to the present invention, molding of the above-mentioned color tone evaluation injection molded plate
When molding is resumed after finishing molding once,
Therefore, the number of black foreign matters generated was kept at a low level. [0049] [Table 1] [0050] [Table 2]

──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Hiroaki Kaneko 2-1, Hinode-cho, Iwakuni-shi, Yamaguchi Pref. Teijin Limited Iwakuni Research Center ) Surveyed field (Int.Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (1)

(57) [Claim 1] When producing a polycarbonate by melt-polycondensing an aromatic dihydroxy compound and a diaryl carbonate, (A) a nitrogen-containing basic compound and (B) an alkali metal compound And / or performing a reaction in the presence of a catalyst comprising an alkaline earth metal compound and a hindered phenol compound (C).