JPS6116923A - Production of copolycarbonate resin - Google Patents

Abstract

PURPOSE:A diol ester of hydroxybenzenecarboxylic acid is used as a part of the dihydric phenol to produce the titled resin which has high fluidity and resistance to solvents and is suitably used as a material for precise molding. CONSTITUTION:(A) A bisphenol of formula I (R is 1-15C divalent aliphatic or alicyclic group; X is alkyl, aryl; p, q are 0-2) such as bis(4-hydroxyphenyl)methane (B) a diol of hydroxybenzenecarboxylic acid diester such as ethylene- bis(p-hydroxybenzoate) and, when necessary, a molecular weight regulator are allowed to react with phosgen in an inert solvent such as dichloromethane and an aqueous alkali, then a polymerization catalyst of a tertiary amine is added to effect interfacial polycondensation to give the objective resin. The amount of component B is preferably 5-50mol% based on the total dihydric phenols.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a method for producing a new copolycarbonate resin with excellent fluidity and solvent resistance, and the copolycarbonate resin produced by this method takes advantage of its properties. Therefore, it can be suitably used for precision molding materials, molding materials, films or sheets, and various other uses.

[Conventional methods and their problems]

Conventionally, polycarbonate resin has been known as a material with excellent heat resistance, transparency, mechanical strength, electrical properties, and non-toxicity, but it has the drawbacks of insufficient fluidity and solvent resistance. be.

” - As a method to overcome the drawbacks mentioned above and improve fluidity, there is a method of adding a plasticizer to polycarbonate resin (
Special Publication No. 45-39941, Special Publication No. 48-4100
(Japanese Patent Publication No. 52-50078), a method of using a fatty acid having an aliphatic long-chain alkyl group with a plasticizing effect, its chloride, or a long-chain alkylphenol as a molecular weight regulator or terminal stopper (Japanese Patent Publication No. 52-50078) There is a public notice).

In the case of the method using a plasticizer, the fluidity of the polycarbonate resin is improved, but during molding, plasticizer vapor with a unique odor is generated and condenses on the mold surface, causing damage to the molded product. It is transferred onto the surface, causing poor appearance, deterioration of the working environment due to odor, and various other harmful effects. In addition, the method of introducing a long-chain alkyl group at the end of the molecule is as follows:
There are no disadvantages such as odor caused by plasticizers, and the fluidity is considerably improved, but since the amount of long-chain alkyl groups that can be introduced at the terminal is limited, a significant improvement in fluidity cannot be expected, and the resistance As for solvent properties, the improvement is only insufficient.

In addition, as a method for improving solvent resistance, aromatic carboxylic acids such as terephthalic acid and isophthalic acid, or their acid chlorides are added to the manufacturing process of polycarbonate resin.
There is a method of synthesizing so-called polyester carbonate (JP-A-55-25427, JP-A-55-38824, JP-A-56-44092, etc.), and this method significantly improves solvent resistance. However, in this method, because of the aromatic carboxylic acid ester introduced to improve solvent resistance, fluidity was considerably reduced.

[Means for solving problems]

In order to improve the above points, the present inventors have conducted intensive studies and found that by using hydroxybenzenecarboxylic acid diester of diol as part of the dihydric phenol compound, fluidity and solvent resistance can be improved. They have found that both properties are improved, and have completed the present invention.

That is, in producing polycarbonate by a solution method, the present invention uses a hydroxybenzenecarboxylic acid diester of a bisphenol represented by the following general formula (1) and a diol represented by (2) as a dihydric phenol compound. This is a method for producing a copolycarbonate resin with improved fluidity and solvent resistance, characterized by the following: General formula (1): (R in the formula is a divalent aliphatic or alicyclic resin having 1 to 15 carbon atoms. group, or phenyl-substituted alkyl group, or -o-, -
s-, -5o-, -5o2, -CO-, X is an alkyl group, aryl group, or halogen atom, p, q
is an integer from 0 to 2. ) General formula (2): (R' in the formula is a divalent aliphatic, alicyclic, or aliphatic ether group having 2 to 30 carbon atoms, 1, and X is an alkyl group, aryl group, or halogen atoms, and p, , q are integers from O to 2.) In a preferred embodiment,
The amount of the hydroxybenzenecarboxylic acid diester of the diol of general formula (2) is 1 to 95 mol%, particularly 5 to 50 mol%, based on all the dihydric phenols used.

The configuration of the present invention will be explained below.

Among the dihydric phenol compounds of the present invention, general formula +1)
Preferred bisphenols represented by are bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)sulfoxide. hydroxyphenyl) sulfide,
Bis(4-hydroxyphenyl)ketone, 1.1-bis(4-hydroxyphenyl)ethane, 2.2-bis(4
-hydroxyphenyl)propane, 2,2-bis(4-
hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-
Hydroxy-3,5-dibromophenyl)propane, 2
, 2-bis(4-hydroxy-3+5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2゜2-bis(4-hydroxy-3-chlorophenyl)propane, 2, 2-bis (4
-hydroxy-3,5-dimethylphenyl)propane,
Examples include 1.1-bis(4-hydroxyphenyl)-1-phenylethane and bis(4-hydroxyphenyl)diphenylmethane.

In addition, the hydroxybenzenecarboxylic acid diester of the diol represented by -e formula (2) is generally produced by an esterification reaction between hydroxybenzenecarboxylic acids and a diol, and the diols include ethylene glycol, 1,3-propanediol, 1,4
-Butanediol, pentamethylene glycol, ■, 5
-hexanediol, hexamethylene glycol, 1.
7-hebutanediol, 1,8-octanediol, 1
, 9-nonanediol, 1.10-decanediol, 1
, 11-undecanediol, 1.12-dodecanediol, 1.13-) lysocanediol, 1,14
- aliphatic diols such as tetradecanediol, 1,18-octadecanediol; diethylene glycol;
triethylene glycol, tetraethylene glycol,
dipropylene glycol, tripropylene glycol,
Ether diols such as dibutylene gellicol; 1,4
Specific examples include alicyclic diols such as -dihydroxycyclohexane and 1,3-dihydroxycyclohexane, which are good as long as they are present in the ester as a structure after ester formation, and are necessary for the esterification reaction. For the purpose of promoting, for example, it may be in the form of a cyclic ether such as ethylene oxide or other compounds.

In addition, hydroxybenzenecarboxylic acids include meta- or para-hydroxybenzoic acid and derivatives thereof,
Specifically, methyl meta- or para-hydroxybenzoate, ethyl meta- or para-hydroxybenzoate, propyl meta- or para-hydroxybenzoate, and nuclear substitutions in which the benzene nucleus contains a lower alkyl group, halogen, etc. Examples include meta- or para-hydroxybenzoic acids.

The manufacturing method of the polycarbonate resin of the present invention is different from that of the conventional manufacturing method of polycarbonate resin.
The method for producing polycarbonate resins may be the same as the method for producing polycarbonate resins by conventionally known solution methods such as interfacial polymerization or pyridine methods, except that the hydroxybenzenecarboxylic acid diester of diol () is used as part of the dihydric phenol. That is,
In the interfacial polymerization method, the dihydric phenol compounds of the general formulas (1) and (2) and a molecular weight regulator are added in the presence of an inert organic solvent and an aqueous alkali solution, and these are reacted with phosgene to complete the reaction. Thereafter, a tertiary amine and a quaternary ammonium salt are added as a polymerization catalyst, and interfacial polymerization is performed to obtain a polycarbonate resin copolymer.

In addition, in the pyridine method, the dihydric phenol of the above general formula +11, (2) and the molecular weight regulator are dissolved in pyridine or a mixed solvent of pyridine and an inert solvent, and phosgene is blown into this solution to directly dissolve the polycarbonate resin. This is a method for obtaining copolymers.

In addition, in the above method, depending on the type of dihydric phenol of general formula (11 or (2)) and its usage ratio, the solubility of these compounds in the inert solvent may be insufficient, and in this case, In particular, first the dihydric phenol of the general formula (1) is reacted with phosgene, and then the reaction of the general formula (2) is carried out.
It is also possible to add a dihydric phenol of the general formula (2).
The dihydric phenol of formula (1) is first reacted with phosgene, and then the dihydric phenol of the general formula (1) is added, or the reaction is carried out in a diluted system.For example, dihydric phenol f
In the synthesis of a copolymer containing 80 mol% or less of 11 and 20 mol% or more of dihydric phenol (2), the amount of dihydric phenol (11 and (2) used is larger than that of simultaneous addition before the reaction with phosgene). It is preferable to first phosgenate the dihydric phenol and then add the dihydric phenol, which is used in a small amount, to carry out polymerization.

Incidentally, examples of solvents inert to the reaction used in the polymerization reaction include dichloromethane, 1,2-dichloroethane, 1°1.2.
2-tetrachloroethane, chloroform, 1,1°t-
trichloroethane, carbon tetrachloride, monochlorobenzene,
Examples include chlorinated hydrocarbons such as dichloroenzene; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and ether compounds such as diethyl ether; two or more of these organic solvents are used in combination. You can also do that. In addition, if desired, the water-immiscible solvents listed above can be used in combination with solvents that have an affinity for water, such as ethers, ketones, esters, and nitriles other than those listed above. The mixing ratio must be within a range where the mixed solvent system is not completely miscible with water.

The molecular N regulator used in the present invention is a conventionally known monovalent aromatic hydroxyl compound, such as t- and p-methylphenol, m- and p-propylphenol, bromophenol, tribromophenol, p-tert -Butylphenol and long chain alkyl substituted phenols, long chain alkyl acid chlorides, etc. are used.

As the polymerization catalyst, known tertiary amines and quaternary ammonium salts are used. Specific examples include trimethylamine, triethylamine, tributylamine,
Tertiary amines such as tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline, trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylhensyl ammonium chloride, Examples include quaternary ammonium salts such as triethylhensyl ammonium chloride.

In addition, in the present invention, along with the above dihydric phenol,
A trifunctional organic compound having a phenolic OH group can also be added to form a branched polycarbonate resin. Examples of trifunctional organic compounds include phloroglycin, 2
,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutene-3,4,6-dimethyl-2.4.6
-1-li(4-hydroxyphenyl)hebutene-2
, L3,5-tri(2-hydroxyphenyl)penzole, 1.1.1-)li(4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylfluor Enol, α, α1゜α
″-tri(4-hydroxyphenyl)-1,3,5-
) polyhydroxy compounds exemplified by lyisopropylbenzene, and 3,3-bis(4-hydroxyaryl)oxindole (-isatinbisphenol),
5-chloroisatin, 5.7-dichlorisatin, 5-
Bromyisatin etc. are exemplified, and general formulas (1) and (2)
The amount of the trifunctional or higher polyfunctional organic compound having a phenolic hydroxyl group, which is a branching agent, is usually 0.01 to 3 mol%, preferably 0.1 to 3 mol%, based on the total dihydric phenol compounds in
It is used in a range of 1.0 mol%.

The fluidity during molding of the copolycarbonate resin produced by the production method of the present invention or the solvent resistance of the molded product are as follows:
It is mainly determined by the achieved molecular weight, the type of aliphatic chain of the diol diester represented by the above general formula (2), and the usage ratio of dihydric phenol in the general formulas (1) and (2).

That is, by appropriately selecting and combining the amount of the molecular weight regulator, the number of carbon atoms in the aliphatic chain of the dihydric phenol (2), and the amount of the dihydric phenol (2), desired fluidity and solvent resistance can be achieved. A resin having the following properties is obtained.

Here, the number of carbon atoms in the aliphatic chain of the diol hydroxybenzene carboxylic acid diester of the general formula (2) is 2 to 2.
30, preferably 2-10. If the number of carbon atoms exceeds 30, depending on the amount used, it becomes difficult to wash the polymerization solution with water due to emulsification of the system, and heat resistance decreases, which is not preferable. In addition, the amount of diol diester of general formula (2) used is usually preferably in the range of 1 to 95 mol% of the total dihydric phenol, and if it is used in excess of 95 mol%, the length of the aliphatic chain may also be affected. However, at 1 ffl, the heat resistance tends to decrease, which is not preferable. In particular, a range of 5 to 50 mol % is preferable from the viewpoint of taking advantage of the heat resistance of the polycarbonate resin and improving solvent resistance.

In addition, the molecular weight of the copolycarbonate resin produced by the production method of the present invention is phenol:tetrachloroethane-1
= 1 mixed solvent, the intrinsic viscosity at 25°C [η is 0.
From the viewpoint of mechanical strength and fluidity, it is preferable that the angle is in the range of 3 to 2.0, preferably 0.4 to 1.0.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Comparative Example-1 3.1 kg of sodium hydroxide was dissolved in 426 ml of water, and 20
While maintaining the temperature at °C, 7.3 kg of 2.2-bis(4-hydroxyphenyl)propane (=flP8) and 8 g of hydrosulfide were dissolved.

To this, methylene chloride 281 was added and while stirring, bara-tertiary-butylphenol (=TBP) 18
0 g was added and then 3.5 liters of phosgene was bubbled with +r over 60 minutes.

After the phosgene injection was completed, the reaction solution was vigorously stirred to emulsify it. After emulsification, 8 g of triethylamine was added and the mixture was stirred for about 1 hour to allow polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeated washing with water until the pH of the washing solution became neutral, 357! In addition, the polymer was precipitated. The precipitate was filtered and then dried to obtain a white powdery polycarbonate resin.

Next, this polycarbonate resin was bentoyed for 40 minutes.
A pellet was obtained by extrusion using an extruder at a temperature of 240 to 260°C.

Table 1 shows the results of tests on viscosity, flow value, solvent resistance, etc. using these pellets.

Comparative Example-2, 3 The dihydric phenol used was replaced with B and PA, and 1゜1-
Bis(4-hydroxyphenyl)cyclohexane (=B
PZ) 8.6 kg (Comparative Example-2), bis(4-hydroxydiphenyl)sulfone (=Bl'S) 8. Okg
(Comparative Example-3) The procedure was the same as Comparative Example-1 except for the following. The results are shown in Table 1.

Example-1 3.7 kg of sodium hydroxide was dissolved in 42 Il of water,
6.2 kg of BPA, ethylene-bis(p-hydroxybenzoate) (=EBHB) while keeping at 20℃
1.45kg, 8g of hydrosulfide? I understand.

Add methylene chloride 281 to this and while stirring, T
Add 455g of BP, then add 3.5kg of phosgene to 60g.
It blew in minutes.

After the phosgene injection was completed, the reaction solution was vigorously stirred to emulsify it. After emulsification, 8 g of triethylamine was added and the mixture was stirred for about 1 hour to allow polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeated washing with water until the pH of the washing solution became neutral, 3 times of isopropanol was added. M was added to precipitate the polymer. The precipitate was filtered and then dried to obtain a white powdery polycarbonate resin.

Next, we made this polycarbonate resin into vented 401
A pellet was obtained by extrusion using a single extruder at a temperature of 240 to 260°C.

Table 1 shows the results of tests on viscosity, flow value, solvent resistance, etc. using these pellets.

Examples-2 to 5 In Example-1, from B P A 6.2 ktr to 5
．． 47, and changed the EBHB from 1.45kg to 2. 12kg (Example-2), BBHBl
, 45 kg to 1.58 kg of butylene-bis(p-hydroxybenzoate) (-〇BHB) (
Example-3), BPA 6.2 kg to 5.47 k
g, E B HB 1.45kg to BB) (8
1,58 kg (Example-4), BPA6.2
Example 1 except that the E B HB was changed from 6.57 kg to 6.57 kg, and 1.45 kg of E B HB was changed to 1.24 kg of octylene bis(p-hydroxybenzoate) (=OBHB) (Example 5). I did the same. The results are shown in Table 1.

Example-6 3.7 kg of sodium hydroxide was dissolved in 42β of water,
BPZ 4.29kg, EB while keeping at 20℃
HB 4.83 kg, hydrosulfide 8g?
I understand.

This includes methylene chloride 287! was added, 180g of TBP was added while stirring, and then 3.5kg of phosgene was added to the
I blew it in 0 minutes.

After the phosgene injection was completed, the reaction solution was vigorously stirred to emulsify it. After emulsification, 8 g of triethylamine was added and the mixture was stirred for about 1 hour to allow polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeating water washing until P)I in the washing solution became neutral, 35N of isopropanol was added. The polymer was precipitated. The precipitate was filtered and then dried to obtain a white powdery polycarbonate resin.

Next, we made this polycarbonate resin into a vented 40*
Pellets were obtained by extrusion using a vs extruder at a temperature of 240-260°C.

Table 1 shows the results of tests on viscosity, flow value, solvent resistance, etc. using these pellets.

Examples 7 and 8 In Example 6, BPZ was added from 4.29 kg to 5.
Change to 57 kg, replace EBHB with BBHB 3 months
．． 1 kg (Example-7), BPZ was 4.2
The weight was changed from 9 kg to 6.86 kg, and EBHB was replaced with HBHB to 2.29 k+r (Example-
8) The rest was the same as in Example-6. The results are shown in Table 1.

Example-9 3.7 kg of sodium hydroxide was dissolved in 42β of water, and 20
While maintaining the temperature at °C, 5.6 kg of BPS and 8 g of hydrosulfide were dissolved.

Add 28 n of methylene chloride to this, add 180 g of TBP while stirring, and then add 3.5 kg of phosgene to 6
I blew it in 0 minutes.

After finishing blowing phosgene, add 2.9 kg of EB HB, stir vigorously to emulsify the reaction solution, and after emulsification, add 8 g of EB HB.
of triethylamine was added and stirred for about 1 hour, followed by polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeated washing with water until the pH of the washing solution became neutral, 357! In addition, the polymer was precipitated. The precipitate was filtered and then dried to obtain a white powdery polycarbonate resin.

Next, this polycarbonate resin was made into a vented 4Qm
Pellets were obtained by extrusion using an M extruder at a temperature of 240 to 260°C.

Table 1 shows the results of tests on viscosity, flow value, solvent resistance, etc. using these pellets.

Example-10 In Example-9, BPS was changed from 5.6 kg to 6.0 kg.
Change to 4kg and replace EBHB with BBHB 2.1
The same procedure as Example 9 was carried out except that the weight was 1 kg. The results are shown in Table 1.

In Table 1, 0BIIB: nioctiton-bis(11-lahydroxybenthoate), 11BHB: hexylene-bis(baraxylene-benthoate).

Amount used: f21/(on 2+) X100 (mol χ).

[Operation and effects of the invention]

As described above, the copolycarbonate resin produced by the method of the present invention has lower melt viscosity, significantly improved fluidity, and excellent solvent resistance compared to conventional polycarbonate resins. . Therefore, according to the present invention, molding, which was conventionally considered difficult, can be easily performed, the molding temperature can be lowered even in normal molding, and thermal decomposition of the resin during molding is significantly suppressed. This material is suitable for precision molding, etc. Furthermore, the obtained molded product has excellent solvent resistance, so it can be used in such applications and solvent-resistant applications such as automobile parts, and can also be used in other forms, such as film or sheet materials. It is useful.

Patent applicant Mitsubishi Gas Chemical Co., Ltd. Representative Kazusho Nagano

Claims (1)

[Claims] 1. In producing polycarbonate by a solution method, bisphenol represented by the following general formula (1) and hydroxybenzenecarboxylic acid diester of diol represented by (2) are used as dihydric phenol compounds. A method for producing a copolycarbonate resin with improved fluidity and solvent resistance, characterized by using. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (R in the formula is a divalent aliphatic group having 1 to 15 carbon atoms, alicyclic group, or phenyl substitution) Alkyl group, or -O-, -S-, -SO-, -SO_2-
, -CO-. X is an alkyl group, an aryl group, or a halogen atom, and p and q are integers of 0 to 2. ) General formula (2): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) (R' in the formula is a divalent aliphatic group having 2 to 30 carbon atoms, alicyclic group, or (It is an aliphatic ether group, X is an alkyl group, an aryl group, or a halogen atom, and p and q are integers of 0 to 2.) 2. Hydroxybenzenecarboxylic acid diester of diol of general formula (2) 2. The method for producing a copolycarbonate resin according to item 1, wherein the amount used is in the range of 1 to 95 mol % based on all dihydric phenols used. 3. The method for producing a copolycarbonate resin according to item 1, wherein the amount of the hydroxybenzenecarboxylic acid diester of the diol of general formula (2) is in the range of 5 to 50 mol% based on all the dihydric phenols used. .