JPH09100348A - Production of polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polycarbonate resin having a low photoelastic constant and a low water absorptivity and excellent heat stability in good yields. SOLUTION: In producing a polycarbonate resin by reacting a dihydric phenol based on 4,4'-(p-phenylenediisopropylidene)diphenol with phosgene, the dihydric phenol is used in the form of a solution in an aqueous potassium hydroxide, and the solution is reacted with phosgene in the presence of an inert organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polycarbonate resin. More specifically, it relates to a method for efficiently producing a polycarbonate resin having low birefringence and water absorption and excellent thermal stability.

[0002]

2. Description of the Related Art Polycarbonate resins derived from bisphenol A obtained by reacting phosgene with 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), which has heretofore been known as a typical polycarbonate resin, are Excellent transparency, heat resistance, mechanical properties,
Further, it has many excellent properties such as good dimensional accuracy and is therefore used as an engineering plastic in many fields. Further, in recent years, its transparency has been utilized to expand its application to the fields of optical disks, optical fibers, lenses, etc., and in particular, it is widely used as a material for substrates for information recording media in the field of optical disks. However, the polycarbonate resin from bisphenol A has a large photoelastic constant due to the optical anisotropy of the benzene ring, and thus has a drawback that the birefringence of the substrate is large, and improvement thereof is demanded. Further, due to the tendency of higher density of the substrate, its warpage becomes a problem, and there is a demand for a polycarbonate resin substrate having further less warpage. This warpage is caused by the difference in the amount of water absorption between the front and back of the substrate due to the presence of the metal film provided on the substrate, and the greater the water absorption rate of the polymer, the greater the warpage. Therefore, the appearance of a polycarbonate resin having a low photoelastic constant and a low water absorption is desired. On the other hand, 4,4'-
It is known that when (p-phenylene diisopropylidene) diphenol is reacted with phosgene, a polycarbonate resin having a low photoelastic constant and a low water absorption can be obtained (Japanese Patent Publication No. 39-96). However, this polycarbonate resin is not yet commercially available.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polycarbonate resin having a low photoelastic constant and a low water absorption rate and excellent thermal stability in a high yield.

The inventor of the present invention aims to achieve the above-mentioned object.
Polycarbonate resin from 4 '-(p-phenylenediisopropylidene) diphenol was added to bisphenol A.
An attempt was made to produce it by an interfacial polycondensation reaction which is usually used for the polycarbonate resin and the like from No. 1, but the yield was remarkably low, and only a polymer having poor thermal stability and no practical use was obtained. In addition, it was tried to produce a copolymer with other dihydric phenol, but it was difficult to synthesize a copolymer having an arbitrary composition ratio due to its poor reactivity. Therefore, the present inventor has conducted extensive studies to solve these problems, and as a result, replaces the sodium hydroxide aqueous solution usually used in the interfacial polycondensation reaction of the conventional polycarbonate resin with an aqueous potassium hydroxide solution having a specific concentration. Using a certain amount,
It was also found that all of the above problems can be solved by controlling the molar ratio of phosgene within a certain range to carry out the phosgenation reaction. The present invention has been completed based on this finding.

[0005]

The present invention provides 4,4'-
In producing a polycarbonate resin by reacting a dihydric phenol mainly containing (p-phenylenediisopropylidene) diphenol with phosgene, the dihydric phenol is used as an aqueous potassium hydroxide solution and in the presence of an inert organic solvent. Is a method for producing a polycarbonate resin, which comprises reacting with phosgene.

The dihydric phenol used in the present invention is 4,
4 '-(p-Phenylenediisopropylidene) diphenol is a main object, and dihydric phenols other than 4,4'-(p-phenylenediisopropylidene) diphenol, such as hydroquinone, are used as long as the object of the present invention is not impaired. , Resorcin, 4,4'-dihydroxydiphenyl,
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 4,4 '-(m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -3,3 , 5-Trimethylcyclohexane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl Sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide and the like can be used in combination. Particularly, 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 4,4 '-(m-phenylenediisopropylidene) diphenol are preferable, and when these are used in an amount of 10 to 50 mol%, they are obtained. The melt flowability of the obtained polycarbonate resin is improved, and the moldability is improved. Also, a small amount of trifunctional compound can be used as a branching agent. Further, a part of bisphenol can be replaced with dicarboxylic acid.

In the interfacial polycondensation reaction of the present invention, first, a phosgenation reaction is carried out. The phosgenation reaction was carried out by adding 4,4 '-(p-phenylenediisopropylidene) to an aqueous solution of potassium hydroxide.
Dissolve diphenol and add an inert organic solvent to it to add 3
While maintaining the temperature at 0 ° C or lower, preferably 15 to 25 ° C, phosgene is reacted and then subjected to a polycondensation reaction. To copolymerize another dihydric phenol, another dihydric phenol is also dissolved when an aqueous potassium hydroxide solution of 4,4 '-(p-phenylenediisopropylidene) diphenol is prepared, and an inert organic solvent is used. Is added to give a phosgenation reaction and then subjected to a polycondensation reaction, or a potassium hydroxide aqueous solution of 4,4 ′-(p-phenylenediisopropylidene) diphenol and another dihydric phenol potassium hydroxide aqueous solution are separately prepared. The phosgenation reaction is effected by adding an inert organic solvent to each of them, and the resulting oligomers are mixed and subjected to a polycondensation reaction.

If the amount of potassium hydroxide used here is too small, the phosgenation reaction is difficult to proceed and the molecular weight is difficult to increase, and if it is too large, the decomposition of phosgene increases, so the molar ratio to phosgene is 2. 5-
4.5 is suitable, and 3.0 to 4.0 is particularly preferable.
Further, if the potassium hydroxide concentration in the aqueous potassium hydroxide solution is too low, the solubility of the dihydric phenol will decrease, and the reaction efficiency will deteriorate, and if it is too high,
During the phosgenation reaction or the polycondensation reaction, the decomposition of the chloroformate terminal increases and the molecular weight becomes difficult to increase, so 3 to 15% by weight is suitable, and 5 to 10% by weight is particularly preferable. The amount of dihydric phenol in the aqueous potassium hydroxide solution is usually selected in the range of 0.5 to 20% by weight, preferably 5 to 15% by weight. Further, the water used for the potassium hydroxide aqueous solution is preferably ion-exchanged water, and the potassium hydroxide aqueous solution is preferably deoxidized through nitrogen gas before use.

As the inert organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used, and methylene chloride is particularly preferably used. The amount of the inert organic solvent used is appropriately 10 to 35, and particularly preferably 20 to 30, in terms of molar ratio to the total amount of the dihydric phenol. An inert organic solvent is also preferably deoxidized and used in the same manner as the potassium hydroxide aqueous solution.

To react phosgene with an alkaline aqueous solution of a dihydric phenol, gaseous phosgene may be blown or liquid phosgene may be mixed. When the reaction temperature exceeds 30 ° C., decomposition of the terminal chloroformate increases, and the thermal stability of the obtained polycarbonate resin deteriorates. If the amount of phosgene used is too small, it will be difficult to obtain a polycarbonate resin having a sufficient degree of polymerization because the amount of phosgene involved in the reaction will be insufficient.If it is too large, a large amount of terminal chloroformate will remain or this terminal chloroformate will be hydrolyzed. As a result, the amount of terminal OH increases and the thermal stability of the resulting polycarbonate resin deteriorates. Therefore, the molar ratio to the total amount of dihydric phenol should be in the range of 1.15 to 1.50, and particularly 1 The range of 0.2-1.35 is preferable. During the reaction, it is preferable to keep the pH at 10 or more, and a small amount of a reducing agent such as hydrosulfite may be added during the phosgenation.

The subsequent polycondensation reaction is usually 20-40.
C., preferably 25 to 35.degree. C. The reaction time is usually several minutes to 5 hours, preferably 30 minutes to 1 hour. It is preferable to maintain the pH at 12 or higher during the reaction. Also, a small amount of an amine-based catalyst can be used to promote the reaction. Examples of preferred catalysts include tertiary amines and quaternary ammonium compounds such as triethylamine, trimethylamine, triethylammonium bromide, and triethylammonium hydroxide, and the amount thereof is usually 0.0001 to 0.01 in terms of molar ratio to the total amount of bisphenol, Preferably 0.001-
It is 0.005. The degree of polymerization of the polycarbonate resin thus obtained becomes brittle in the obtained molded product when it is too small, and the melt fluidity becomes poor when it becomes too large,
It is difficult to obtain a good molded product, so 0.7 g of polymer
Is preferably dissolved in 100 ml of methylene chloride and the specific viscosity measured at 20 ° C. is in the range of 0.2 to 0.4.

Further, monofunctional phenols which are usually used as an end terminating agent can be used. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resin is end-capped with monofunctional phenols,
It has better thermal stability than those that do not. Such monofunctional phenols may be those used as a terminal stopper of the polycarbonate resin, generally phenol or lower alkyl-substituted phenol,
The monofunctional phenols represented by the following general formula (2) can be shown.

[0013]

Embedded image

[Wherein A is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 9 carbon atoms, preferably 1 to 8 carbon atoms, r is 1 to 5, preferably an integer of 1 to 3] Specific examples of such monofunctional phenols Examples include, for example, phenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol and the like. These monofunctional phenols should be at least 5 relative to all terminals of the obtained polycarbonate resin.
It is desirable to introduce at mol%, preferably at least 10 mol% terminals.

Further, when the end groups of the polycarbonate resin are blocked by using phenols, benzoic acid chlorides or long-chain alkylcarboxylic acid chlorides having a long-chain alkyl group or an aliphatic polyester group as a substituent,
Similar to the monofunctional phenols, these not only function as a terminal terminating agent or a molecular weight modifier, but also serve to modify the obtained polycarbonate resin. That is, these terminal modifiers improve the melt flowability of the resin by binding to the terminals of the polycarbonate resin, not only facilitating the molding process but also improving the physical properties of the molded product. In particular, it has the effect of lowering the water absorption of the resin.

The end modifier is represented by the following general formula (1)

[0017]

Embedded image

[Wherein Q is a halogen atom or a carbon number of 1 to 1]
0 monovalent aliphatic hydrocarbon group, p is an integer of 0 to 4, A is

[0019]

Embedded image

(Where X is a single bond, -R-O-, -R-C
OO- or -RO-CO-, where R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n is 10
An integer of 50),

[0021]

Embedded image

(However, Y is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ¹ is a hydrogen atom, —CO—R ¹ , —CO—
O—R ² or —R ³ , where R ¹ , R ² and R ³ are each a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 4 to 4 carbon atoms.
8 monovalent alicyclic hydrocarbon group or C 6-15 monovalent aromatic hydrocarbon group, q is an integer of 4 to 20, and m is 1 to 1.
00 integer),

[0023]

Embedded image

(However, Z is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ² is a hydrogen atom, and 1 to 1 carbon atoms.
0 divalent aliphatic hydrocarbon group, monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms or monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, q is an integer of 4 to 20, m is an integer from 1 to 100),

[0025]

Embedded image

(However, Y is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ¹ is a hydrogen atom, --CO--R ¹ , --CO--.
O—R ² or —R ³ , where R ¹ , R ² and R ³ are each a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 4 to 4 carbon atoms.
8 monovalent alicyclic hydrocarbon group or C 6-15 monovalent aromatic hydrocarbon group, q is an integer of 4 to 20, and m is 1 to 1.
00 integer),

[0027]

Embedded image

(However, Z is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ² is a hydrogen atom, and 1 to 1 carbon atoms.
0 divalent aliphatic hydrocarbon group, monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms or monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, q is an integer of 4 to 20, m is an integer of 1 to 100)], and is, for example, a general formula (1-a) shown below.

[0029]

Embedded image

[Wherein Q is a halogen atom or a carbon number of 1 to 1]
0 monovalent aliphatic hydrocarbon group, p is an integer of 0 to 4, X is a single bond, -R-O-, -R-CO-O- or -R-O-.
CO-, where R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 10 to 50], and the following general formula (1-b)

[0031]

Embedded image

[Wherein Q and p are the same as in the general formula (1-a), Y is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and W is W].
¹ is a hydrogen ^{atom, -CO-R 1, -CO-} O-R 2 or -
R ³ , wherein R ¹ , R ² and R ³ are each 1 to 10 carbon atoms
Monovalent aliphatic hydrocarbon group, monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms or monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, q is an integer of 4 to 20, m Is an integer from 1 to 100],
The following general formula (1-c)

[0033]

Embedded image

[Wherein Q, p, q and m are represented by the general formula (1-
The same as b), Z is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ² is a hydrogen atom, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and 4 to 12 carbon atoms. 8 monovalent alicyclic hydrocarbon group or C 6-15 monovalent aromatic hydrocarbon group], the following general formula (1-d)

[0035]

Embedded image

[Wherein Q, p, q, m, Y and W ¹ are the same as in the general formula (1-b)] and the general formula (1-e)

[0037]

Embedded image

A monofunctional phenol represented by the formula [wherein Q, p, q, m, Z and W ² are the same as in the general formula (1-c)], and particularly represented by the general formula (1-a). Alkyl-substituted phenols are preferred. Among such alkyl-substituted phenols, those having n of 10 to 30 are preferable. Specific examples of such alkyl-substituted phenols include decylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, eicosylphenol, heneicosylphenol. , Docosylphenol, tricosylphenol, tetracosylphenol, pentacosylphenol, hexacosylphenol, heptacosylphenol, octacosylphenol, nonacosylphenol, triacontylphenol and the like.

If the amount of the monofunctional phenol represented by the general formula (1) is too small, it is difficult to sufficiently improve the melt fluidity of the polycarbonate resin, so that the modified polycarbonate resin obtained has at least all terminals. An amount corresponding to 5 mol% is required. Further, when the amount of the monofunctional phenol used is too large, the glass transition temperature of the modified polycarbonate resin obtained tends to be lowered. Therefore, although it depends on the amount of the aliphatic hydrocarbon group in the monofunctional phenol, It is preferably 50 mol% or less of all terminals. In such a case, the remaining terminals of the polycarbonate resin may be blocked with a monofunctional phenol other than the monofunctional phenol represented by the general formula (1), for example, the monofunctional phenol represented by the general formula (2). Yes, this is also preferable. The addition timing of the monofunctional phenol represented by the general formula (1) and the other monofunctional phenol is not particularly limited as long as the production reaction of the polycarbonate resin is completed, but the phosgenation reaction is not limited. It is preferable to add it at the stage when the process is completed. After adding the monofunctional phenol represented by the general formula (1) and another monofunctional phenol,
The polycarbonate resin production reaction may be continued.

The polycarbonate resin thus obtained can be molded by any method such as an injection molding method, a compression molding method, an extrusion molding method, a solution casting method, and if necessary, for example, a heat stabilizer, an antioxidant, Light stabilizer,
Additives such as a coloring agent, an antistatic agent, a lubricant, and a release agent can be added.

[0041]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. In the examples, parts and% are parts by weight and% by weight, respectively. (1) Specific viscosity; 0.7 g of polymer was added to 100 methylene chloride.
It was dissolved in ml and measured at 20 ° C. (2) Glass transition temperature (Tg); measured at 10 ° C./min using a 910 type DSC manufactured by DuPont. (3) Weight loss starting temperature: A 5% weight loss starting temperature and a 10% weight loss starting temperature were measured using a DuPont 951 type TGA. (4) Melt fluidity (MFR); measured according to JIS-K7210 (test temperature: 280 ° C., test load: 2.
16 kgf). (5) Water absorption rate: Measured by molding a press plate according to JIS-K7209. (6) Photoelastic constant: Measured using a photoelasticity measuring device PA-150 manufactured by Riken Keiki Co., Ltd.

Example 1 A reactor equipped with a thermometer, a stirrer, and a phosgene blowing tube was charged with 840.0 parts of ion-exchanged water and 58.8 parts of potassium hydroxide, and 4,4 'was added thereto.
After dissolving 48.4 parts of-(p-phenylenediisopropylidene) diphenol, 23.9 parts of 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 0.15 part of hydrosulfite, methylene chloride was dissolved. 555.0 parts were added, and 30.0 parts of phosgene was blown thereinto under stirring at 18 to 21 ° C. over about 35 minutes. After finishing blowing phosgene, p-te
After adding 1.75 parts of rt-butylphenol and further adding 0.08 part of triethylamine to emulsify, 26-33 ° C
After stirring for 1 hour, the reaction was completed. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase was almost the same as that of ion-exchanged water, the organic phase was separated and methylene chloride was evaporated. While crushing, 77.7 parts of powdery polymer (yield 9
7%). The evaluation results of this polymer are shown in Table 1.

[Comparative Example 1] The reactor used in Example 1 was charged with 860.0 parts of ion-exchanged water and 71.1 parts of a 48.5% sodium hydroxide aqueous solution, and 4,4 '-(p-
Phenylene diisopropylidene) diphenol 48.4
Part, 2,2-bis (3-methyl-4-hydroxyphenyl) propane 23.9 parts and hydrosulfite 0.
After dissolving 15 parts, 590.0 parts of methylene chloride was added, and 30.0 parts of phosgene was added to about 55 parts at 18 to 21 ° C. under stirring.
It took minutes to blow. 48.5 after finishing blowing phosgene
% Aqueous sodium hydroxide solution (15.4 parts) and p-tert-butylphenol (1.75 parts) were further added, and triethylamine (0.08 part) was added to emulsify the mixture, followed by stirring at 26 to 33 ° C. for 1 hour to complete the reaction. After the completion of the reaction, the same procedure as in Example 1 was carried out to obtain 57.7 parts of a powdery polymer.
The evaluation results of this polymer are shown in Table 1. As is clear from the table, in the method using sodium hydroxide, not only the yield was remarkably low at 72%, but also the 10% weight loss starting temperature was low and the heat resistance was poor.

[Example 2] The reactor used in Example 1 was charged with 840.0 parts of ion-exchanged water and 58.8 parts of potassium hydroxide, and 4,4 '-(p-phenylenediisopropylidene) was added thereto. 64.5 parts diphenol, 4,4 '-(m
-Phenylenediisopropylidene) diphenol 16.
After dissolving 1 part and 0.16 part of hydrosulfite, 555.0 parts of methylene chloride was added, and the mixture was stirred at 18 to 21 ° C.
Then, 30.0 parts of phosgene was blown in in about 40 minutes. After blowing phosgene, p-tert-butylphenol 2.1
After adding 0 part and further adding 0.08 part of triethylamine to emulsify, the mixture was stirred at 26 to 33 ° C. for 1 hour to complete the reaction. After completion of the reaction, the same procedure as in Example 1 was carried out to obtain 84.8 parts (yield 96%) of a powdery polymer. The evaluation results of this polymer are shown in Table 1.

Comparative Example 2 The reactor used in Example 1 was charged with 860.0 parts of ion-exchanged water and 56.7 parts of a 48.5% sodium hydroxide aqueous solution, and 4,4 '-(p-phenylene diene) was added. 64.5 parts of isopropylidene) diphenol,
4,4 '-(m-phenylenediisopropylidene) diphenol 16.1 parts and hydrosulfite 0.17
After the parts were dissolved, 590.0 parts of methylene chloride was added, and 30.0 parts of phosgene was blown thereinto under stirring at 18 to 21 ° C over about 55 minutes. After the completion of blowing phosgene, 14.4 parts of a 48.5% sodium hydroxide aqueous solution and 1.40 parts of p-tert-butylphenol were added, and triethylamine 0.08 was added.
After adding a part and emulsifying, it stirred at 26-33 degreeC for 1 hour, and reaction was complete | finished. After the completion of the reaction, the same operation as in Example 1 was carried out to obtain 61.0 parts of a powdery polymer. The evaluation results of this polymer are shown in Table 1. As is clear from the table,
With this method using sodium hydroxide, the yield is 69%.
It was remarkably low, about 20% of the monomer was recovered, both the specific viscosity and the glass transition temperature were low, and the weight loss onset temperatures of 5% and 10% were both low, and only poor heat resistance was obtained.

Example 3 The reactor used in Example 1 was charged with 840.0 parts of ion-exchanged water and 58.8 parts of potassium hydroxide to prepare 4,4 '-(p-phenylenediisopropylidene) diphenol. After dissolving 80.7 parts and 0.17 part of hydrosulfite, 555.0 parts of methylene chloride was added, and 30.0 parts of phosgene was added to about 4 parts at 18 to 21 ° C. under stirring.
It took 0 minutes to blow. After completion of blowing phosgene p-tert
-Butylphenol 1.57 parts and 1.97 parts of an alkyl-substituted phenol having about 23 carbon atoms (a mixture of ortho-substituted 70% and para-substituted 30%) were added, and 0.08 part of triethylamine was further added to emulsify. After making it 26-33 ℃
After stirring for 1 hour, the reaction was completed. After completion of the reaction, the same procedure as in Example 1 was carried out to obtain 85.8 parts (yield: 95%) of a powdery polymer. The evaluation results of this polymer are shown in Table 1.
It was shown to.

Comparative Example 3 The reactor used in Example 1 was charged with 860 parts of ion-exchanged water and 71.1 parts of a 48.5% sodium hydroxide aqueous solution, and 4,4 '-(p-phenylene diisopropylidene) was added. ) After dissolving 80.7 parts of diphenol and 0.17 part of hydrosulfite, 590 parts of methylene chloride was added, and 30 parts of phosgene was blown thereinto under stirring at 18 to 21 ° C over about 40 minutes. After finishing blowing phosgene,
15.4 parts of 48.5% sodium hydroxide aqueous solution, p-te
1.57 parts of rt-butylphenol and about 23 carbon atoms
1.97 parts of the alkyl-substituted phenol (a mixture of ortho-substituted 70% and para-substituted 30%) was added, and 0.08 part of triethylamine was further added to emulsify the mixture and then the mixture was added to 26-33.
The reaction was completed by stirring at 1 ° C. for 1 hour. After the completion of the reaction, the same operation as in Example 1 was carried out to obtain 58.7 parts of a powdery polymer. The evaluation results of this polymer are shown in Table 1. As is clear from the table, with this method using sodium hydroxide, the yield was extremely low at 65%, about 30% of the monomer was recovered, the specific viscosity was low, and the polymerization reaction did not proceed sufficiently.

Example 4 The reactor used in Example 1 was charged with 840.0 parts of ion-exchanged water and 58.8 parts of potassium hydroxide to prepare 4,4 '-(p-phenylenediisopropylidene) diphenol. After dissolving 80.7 parts and 0.17 part of hydrosulfite, 555.0 parts of methylene chloride was added, and 30.0 parts of phosgene was added to about 4 parts at 18 to 21 ° C. under stirring.
It took 0 minutes to blow. After completion of blowing phosgene p-tert
-Butylphenol 1.57 parts and a reaction product of caprolactone with m-hydroxybenzyl alcohol (molar ratio 1 /
5) 4.04 parts was added, and further triethylamine 0.08
After adding a part and emulsifying, it stirred at 26-33 degreeC for 1 hour, and reaction was complete | finished. After the completion of the reaction, the same operation as in Example 1 was carried out to obtain 86.5 parts (yield 96%) of a powdery polymer. The evaluation results of this polymer are shown in Table 1.

[Reference Example] For reference, the specific viscosity is 0.28.
Table 1 shows the evaluation results of the polycarbonate resin prepared from Bisphenol A of No. 4 in Table 1. As is clear from the table, both the water absorption rate and the photoelastic constant are high, and the superiority of the polymer obtained in the present invention in optical applications is clear.

[0050]

[Table 1]

[0051]

According to the present invention, a dihydric phenol mainly containing 4,4 '-(p-phenylenediisopropylidene) diphenol has a low water absorption coefficient and a low photoelastic constant, excellent optical characteristics, and excellent heat resistance. A polycarbonate resin having excellent stability can be efficiently produced, and by using a specific monofunctional phenol as an end terminating agent, a polycarbonate resin having excellent melt fluidity and moldability can be efficiently produced. Yes, and the industrial effect it produces is exceptional.

Claims (15)

[Claims] 1. A dihydric phenol mainly containing 4,4 '-(p-phenylenediisopropylidene) diphenol is reacted with phosgene to produce a polycarbonate resin. And a method for producing a polycarbonate resin, which comprises reacting with phosgene in the presence of an inert organic solvent. 2. The method for producing a polycarbonate resin according to claim 1, wherein the amount of potassium hydroxide used is 2.5 to 4.5 in terms of molar ratio to phosgene. 3. The method for producing a polycarbonate resin according to claim 1, wherein the potassium hydroxide concentration in the aqueous potassium hydroxide solution is 3 to 15% by weight. 4. The method for producing a polycarbonate resin according to claim 1, wherein the amount of phosgene used is 1.15 to 1.50 in terms of molar ratio with respect to the total amount of dihydric phenol. 5. The method for producing a polycarbonate resin according to claim 1, wherein the inert organic solvent is methylene chloride. 6. The use amount of the inert organic solvent is 10 to 35 in a molar ratio with respect to the total amount of the dihydric phenol.
6. The method for producing a polycarbonate resin according to any one of items 1 to 5. 7. The dihydric phenol is 4,4 '-(p-phenylenediisopropylidene) diphenol 50-90.
Mol% and 2,2-bis (3-methyl-4-hydroxyphenyl) propane 50 to 10 mol%.
7. The method for producing a polycarbonate resin according to any one of 6 above. 8. The dihydric phenol is 4,4 '-(p-phenylenediisopropylidene) diphenol 50-90.
Mol% and 4,4 '-(m-phenylenediisopropylidene) diphenol 50 to 10 mol%.
7. The method for producing a polycarbonate resin according to any one of 6 above. 9. A polycarbonate resin obtained from phosgene and a dihydric phenol mainly containing 4,4 ′-(p-phenylenediisopropylidene) diphenol and an amount corresponding to at least 5 mol% based on all terminals of the polycarbonate resin. The following general formula (1): [In the formula, Q is a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 4, and A is (However, X is a single bond, -R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or a carbon number of 1 to 1.
A divalent aliphatic hydrocarbon group of 0, n is an integer of 10 to 50), and (However, Y is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,
W ¹ is a hydrogen atom, —CO—R ¹ , —CO—O—R ² or —R ³ , where R ¹ , R ² and R ³ each have 1 to 1 carbon atoms.
0 monovalent aliphatic hydrocarbon group, C 4-8 monovalent alicyclic hydrocarbon group or C 6-15 monovalent aromatic hydrocarbon group, q is an integer of 4-20, m is an integer of 1 to 100), (However, Z is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ² is a hydrogen atom, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and one of 4 to 8 carbon atoms. Valent alicyclic hydrocarbon group or monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, q is an integer of 4 to 20, m is an integer of 1 to 100), (However, Y is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,
W ¹ is a hydrogen atom, —CO—R ¹ , —CO—O—R ² or —R ³ , where R ¹ , R ² and R ³ each have 1 to 1 carbon atoms.
0 monovalent aliphatic hydrocarbon group, C 4-8 monovalent alicyclic hydrocarbon group or C 6-15 monovalent aromatic hydrocarbon group, q is an integer of 4-20, m is an integer from 1 to 100), and (However, Z is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, W ² is a hydrogen atom, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and one of 4 to 8 carbon atoms. Alicyclic hydrocarbon group or monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, q is an integer of 4 to 20 and m is an integer of 1 to 100)] A method for producing a polycarbonate resin, which comprises using the dihydric phenol as an aqueous potassium hydroxide solution and reacting it with phosgene in the presence of an inert organic solvent in producing the polycarbonate resin. 10. The terminal stopper is represented by the following general formula (1-a): [In the formula, Q is a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 4, X is a single bond,-
R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 10 to 50. ] The manufacturing method of the polycarbonate resin of Claim 9 which is a terminal terminator represented by these. 11. The use amount of potassium hydroxide in a molar ratio to phosgene of 2.5 to 4.5.
The method for producing a polycarbonate resin according to 0. 12. The method for producing a polycarbonate resin according to claim 9, wherein the potassium hydroxide concentration in the aqueous potassium hydroxide solution is 3 to 15% by weight. 13. The method for producing a polycarbonate resin according to claim 9, wherein the amount of phosgene used is 1.15 to 1.50 in terms of molar ratio with respect to the total amount of dihydric phenol. 14. The method for producing a polycarbonate resin according to claim 9, wherein the organic solvent is methylene chloride. 15. The use amount of the organic solvent is 10 to 35 in a molar ratio with respect to the total amount of the dihydric phenol.
5. The method for producing a polycarbonate resin according to any one of 4 above.