JPS633023A - Production of vinyl-terminated polycarbonate resin - Google Patents

Abstract

PURPOSE:To produce a vinyl-terminated polycarbonate resin useful as a raw material for production of a block copolymer with other resins and as a reactive resin modifier, etc., by a solution process, by using a specific isopropenylphenol as a molecular weight modifier. CONSTITUTION:The objective vinyl-terminated polycarbonate can be produced by using an isopropenylphenol of formula (X<1> is F, Cl, Br, lower alkyl or lower alkyloxy; n is integer of 0-4) as a molecular weight modifier in the production of a polycarbonate resin by a solution process.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is a method for producing a novel polycarbonate resin having a vinyl group at the end. It is suitably used for various purposes such as raw materials for producing block copolymers, reactive resin modifiers, and film materials.

[Conventional methods and their problems]

Conventionally, monohydric phenols such as p-tert-butylphenol and phenol have been used as end-stoppers or molecular weight regulators for polycarbonate resins, and long-chain alkylphenols (Japanese Patent Publication No. 52 -50078) is known to be used.

Polycarbonate resins produced using these conventional molecular weight regulators have their molecular chain ends closed;
Polymer ends are inactive in terms of wood quality. For this reason, when modifying the composition to form a composition with other resins or other fillers, there is a drawback that the partner resin is limited because it is of a simple mixing type.

Further, a polycarbonate block copolymer obtained by obtaining a terminally unsaturated polycarbonate resin and addition-polymerizing it with a vinyl compound is disclosed in Japanese Patent Publication No. 48-25076, and therefore, terminally unsaturated polycarbonate resins are also known. However, the unsaturated group introduced in this invention is an aliphatic compound, which has problems such as heat resistance. Furthermore, an example of vinylphenol is also disclosed, but this compound has extremely high reactivity of the vinyl group, so
It has the disadvantage of gelation during the reaction, and it has been difficult to obtain terminally unsaturated polycarbonate with excellent stability.

[Means for solving problems]

The present inventors have conducted intensive studies on methods to improve the above-mentioned drawbacks, and have found that isopropenylphenol can be used in the same manner as conventional end-stopping agents for polycarbonate resins, has excellent stability, and is compatible with vinyl compounds, etc. The present invention was achieved by discovering that the reaction can be easily carried out.

That is, the present invention uses the following general formula (
This is a method for producing a vinyl-terminated polycarbonate resin characterized by using isopropenylphenol represented by 1).

(xl in the formula represents F, CI, Br, or a lower alkyl group or alkyloxy group, and n represents an integer of O to 4.) Hereinafter, the structure of the present invention will be described.

The method for producing a polycarbonate resin of the present invention is different from the conventional method for producing a polycarbonate resin, except that isopropenylphenol of the above general formula (1) is used as a molecular weight regulator or terminal stopper. A manufacturing method similar to the manufacturing method may be used.

That is, in the interfacial polymerization method, a dihydric phenol compound and the molecular weight regulator are reacted with phosgene in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, and then a tertiary amine or quaternary ammonium salt is added. In the pyridine method, a dihydric phenol compound and the molecular weight regulator are dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is blown into the solution to directly obtain polycarbonate resin. It is. In the interfacial polymerization method, the molecular weight regulator may be added during the polymerization after the phosgenation reaction.

Preferred dihydric phenol compounds of the present invention include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, and bis(4-hydroxyphenyl)methane.
-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-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-', ;chlorophenyl)furopane, 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, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, An example is bis(4-hydroxyphenyl)diphenylmethane.

The isopropenylphenol used as the molecular weight regulator represented by the above general formula (1) is meta- or para-
Isopropenylphenol is preferred, and the amount used is 10 to 0.5 mol% based on the dihydric phenol compound.
, preferably in the range of 7 to 2 mol %, and in the present invention, it is also possible to use a conventionally known molecular weight modifier together with the above compound (11).

Examples of solvents inert to the reaction include dichloromethane, 1,2
- Chlorinated hydrocarbons such as dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, LL, 1-1-dichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons include ether compounds such as diethyl ether, and two or more of these organic solvents may be used in combination. Further, if desired, a solvent having an affinity for water such as ethers, ketones, esters, and nitriles other than those mentioned above may be mixed within the limit that the mixed solvent system is not completely miscible with water.

In addition, as a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline, etc. Examples include quaternary ammonium salts such as ammonium chloride, tetramethylammonium chlorand, and triethylbenzylammonium chloride.

The polycarbonate resin of the present invention is produced with the above-mentioned components as essential, but the branching agent is added in an amount of 0.01 to 3 mol%, especially 0.01 to 3 mol%, based on the dihydric phenol compound mentioned above.
．． A branched polycarbonate can also be obtained by using them together in a range of 1 to 1.0 mol %.

Such branching agents include phloroglycin, 2.6
-Simethyl-2.4.6- Tri(4-hydroxyphenyl)hebutene-3,4,6-cymethyl-2.4.6
- tri(4-hydroxyphenyl)hebutene-2
, L3,5-) IJ (2-hydroxyphenyl)penzole, 1,1.1-)su(4-hydroxyphenyl)ethane, 2,6:bis(2-hydroxy-5-
methylbenzyl)-4-methylfuenol, α, α9
．． α-partri (4-hydroxyphenyl) -1,3
, 5-triisopropylbenzene, etc., and 3,3-bis(4-hydroxyaryl)oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromiisatin, etc. is exemplified.

Since the polycarbonate resin produced by the production method of the present invention has active terminals, it can be easily used as a raw material for copolymerization, or by melt-mixing with other polymers that easily react with this vinyl group. It is suitably used in the production of compositions with resins that are not compatible and cannot be used as useful compositions, and can be used alone or in combination with ordinary polycarbonate resins.

In addition, when manufacturing these compositions, antioxidants, light stabilizers, colorants, inorganic or organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants, and electrostatic charges may be added as necessary. An inhibitor or the like may be used in combination as appropriate.

〔Example〕

Hereinafter, a detailed explanation will be given using Examples and Comparative Examples.

Example-1 3.4 kg of sodium hydroxide was dissolved in 421 parts of water, and 20 kg of sodium hydroxide was dissolved in 421 parts of water.
While maintaining the temperature at °C, 6.6 kg of 2,2-bis(4-hydroxyphenyl)propane (-BPA) and 8 g of hydrosulfide were dissolved.

Add methylene chloride 281 to this, and while stirring, p
- 250 g of isopropenylphenol were added and then 3.3 kg of phosgene was bubbled in 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 repeating water washing until the pH of the washing solution became neutral, 35ff of isopropanol was added to the polymerization solution. was precipitated. The precipitate was filtered and then vacuum dried to obtain a white powdery polycarbonate resin.

The results of measuring the viscosity, etc. of this polycarbonate are shown in Table 1.

Example 2 The procedure of Example 1 was repeated except that p-isopropenylphenol was changed to 128 g of m-isopropenylphenol.

The results are shown in Table 1.

Example-3 In Example-1, BPZ (= L
The procedure was the same except that 7.7 kg of 1-his(4-hydroxyphenyl)cyclohexane) and 148 g of p-isopropenylphenol were used.

The results are shown in Table 1.

Example-4 In Example-1, instead of BPA, BPAp <=
bis(4-hydroxyphenyl)-phenylmethane)
8.4 kg, p-isopropenylphenol 194
The same procedure was used except for changing to g.

The results are shown in Table 1.

Example-5 In Example-1, BPA 3.3 kgXBPZ
The same procedure was used except that the weight was changed to 3.9 kg.

The results are shown in Table 1.

Example-6 In Example-1, BPA 3.3 kg, BP
AP4.2kg, p-isopropenylphenol 12
Same procedure except that it was changed to 8g.

The results are shown in Table 1.

Note that the description in Table 1 is as follows.

[Operation and effects of the invention]

According to the production method of the present invention, a terminal vinyl group-containing polycarbonate resin can be obtained in the same manner as a normal polycarbonate resin production method, and industrialization is extremely easy. In addition, the produced polycarbonate resin containing terminal vinyl groups has excellent stability, and by utilizing the properties of vinyl groups,
It can be easily used as a blend material with resins, for which it was not possible to obtain useful compositions due to poor compatibility using conventional simple mixing methods, and it can also be easily used as a raw material for block copolymers using the vinyl group. It is characterized by being possible.

Claims (1)

[Scope of Claim] A method for producing a vinyl-terminated polycarbonate resin by a solution method, characterized in that isopropenylphenol represented by the following general formula (1) is used as a molecular weight regulator. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (X^1 in the formula represents F, Cl, Br, or a lower alkyl group or an alkyloxy group, and n is (Indicates an integer from 0 to 4.)