JPS634853B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester polycarbonate.

It has been known to make polycarbonate into a copolymer with polyester in order to improve the heat resistance of polycarbonate. As a method for producing this polyester polycarbonate, there is a solution method (Japanese Patent Application Laid-open No. 128992/1982) in which bisphenol A and terephthalic acid chloride are reacted in pyridine, and phosgene is introduced into the reaction mixture for polycondensation. However, since this method uses pyridine, it is not industrially satisfactory in terms of recovery, bad odor, etc. Therefore, as an improved technique, an alkaline aqueous solution of divalent phenols obtained by interfacial polymerization is reacted with an organic solvent solution of terephthalic acid chloride and isophthalic acid chloride to form a polyester oligomer, which is then treated with phosgene and further divalent phenols are reacted. Three-stage polycondensation method (Unexamined Japanese Patent Publication No. 1983-
No. 25427, No. 55-38824) and a method of adding phosgene to polyester oligomers (Japanese Unexamined Patent Application Publication No. 1983-1989).
No. 822, No. 56-823) have been proposed.

However, method (2) requires the polyester oligomer to be phosgenated, and method (2) has drawbacks such as non-uniform composition of the resulting polymer. In any case, the polycarbonate units in the polymers obtained by these methods are monomers or mixtures based on monomers and cannot be adjusted arbitrarily, and furthermore, there are problems in integrating them with the polycarbonate manufacturing process. .

The present invention is a novel polyester polycarbonate in which oligomers, which are intermediates in conventional polycarbonate production, can be used in the production of polyester polycarbonate, no new phosgenation step is required, and the molecular weight of the polycarbonate unit can be arbitrarily controlled. The purpose is to provide a manufacturing method for.

The present invention uses alkaline aqueous solutions of dihydric phenols, saturated aliphatic dibasic acids, halogen-substituted aliphatic dibasic acids, aliphatic dibasic acids containing heteroatoms in the fatty chain, unsaturated aliphatic dibasic acids, aromatic A polymerization degree of 2 to 2 is obtained by mixing with an organic solvent solution of an acid chloride of an acid selected from the group consisting of dicarboxylic acids, aliphatic substituted aromatic dicarboxylic acids, and polycyclic aromatic dicarboxylic acids.
10 hydroxyl group-containing polyester oligomers are prepared, and then a chloroformate group-containing polycarbonate oligomer with a degree of polymerization of 2 to 15 obtained from dihydric phenol and phosgene is added to perform polycondensation. It is.

As the dihydric phenol used in the present invention, for example, 2,2-bis(4-hydroxyphenyl)propane, that is, bisphenol A, is typical, and in addition, bis(4-hydroxyphenyl)methane, 1 , 1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxy-3-t) -butylphenyl)propane, 2,
Bis(hydroxyaryl) such as 2-bis(4-hydroxy-3-bromophenyl)propane
alkanes, bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, dihydroxydiarylethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyphenyl ether, etc. Examples include dihydroxydiarylsulfides such as phenyl sulfide, dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone.

In addition, the alkali used to prepare the alkaline aqueous solution of these dihydric phenols is as follows:
These include sodium hydroxide and potassium hydroxide.
The concentration of divalent phenol in the alkaline aqueous solution is not particularly limited and may be arbitrarily determined.

The acid chloride used in the present invention is usually an acyl dichloride obtained by replacing both OH of two carboxyl groups of various dibasic acids with Cl, and may also include acyl dichlorides of tribasic acids and the like. Here, the organic acids constituting the acid chloride include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid derived from linear paraffinic hydrocarbons. acid, saturated aliphatic dibasic acids such as sebacic acid, and halogen-substituted aliphatic dibasic acids. In addition, aliphatic dibasic acids containing heteroatoms in the fatty chain such as thioglycolic acid and dithioglycolic acid, unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and homophthalic acid. acid, o-phenylene diacetic acid, m-
unsubstituted or aliphatically substituted aromatic dicarboxylic acids such as phenylene diacetic acid, p-phenylene diacetic acid,
Polycyclic aromatic dicarboxylic acids such as diphenic acid and 1,4-naphthalene dicarboxylic acid can also be mentioned. Preferred acid chlorides include terephthalic acid chloride, isophthalic acid chloride, etc.
It can also be used as a mixture. In this case, phthalic acid chloride having a halogen atom or an alkyl group in the nucleus is also included. The solvent for this acid chloride is chloroform, trichloroethane,
There are chlorinated hydrocarbon organic solvents such as methylene chloride and dichloroethylene, and these solvents can also be used in combination with organic solvents such as toluene, kydylene, cyclohexane, dioxane, tetrahydrofuran, and acetone. The concentration of acid chloride is also not particularly limited and can be arbitrarily selected within the range up to saturation concentration.

When the aqueous alkaline solution of divalent phenol and the organic solvent solution of acid chloride are mixed, a polyester oligomer is produced. In this case, the mixing ratio of both is preferably such that dihydric phenol is in excess;
Usually 0.5 to 1 acid chloride to 1 dihydric phenol
Mix at a ratio of 0.95 (molar ratio). Moreover, this esterification reaction is completed in a relatively short time, and usually 5
~40℃ for 0.5-60 minutes, preferably 10-35℃ for 1
It is enough to react for ~20 minutes. In carrying out the esterification reaction, a suitable catalyst such as triethylamine can be used. This esterification reaction results in a polymerization degree of 2 with -OH groups at the end.
~10 polyester oligomers are obtained.

In the present invention, as the next second step, the reaction mixture containing the above polyester oligomer is added with a polymerization degree of 2 to 15.
A chloroformate group-containing polycarbonate oligomer is added to perform polycondensation. As the polycarbonate oligomer used here, an oligomer that is an intermediate in a normal polycarbonate manufacturing process, that is, a process of manufacturing polycarbonate using dihydric phenol and phosgene, can be used. This oligomer usually has a terminal chloroformate group content of 75% or more, with the remainder being -OH groups. Here, the usage ratio of polyester oligomer and polycarbonate oligomer is determined based on the polycondensation reaction system.
It is determined by OH group and Cl group in the range of OH group/Cl group = 0.8 to 1.2. During this reaction, the aqueous dihydric phenol alkali solution may be allowed to coexist if necessary. Furthermore, by adding a suitable organic solvent, monovalent phenol as a molecular weight regulator, and a catalyst (eg, triethylamine), the polycondensation reaction can be carried out efficiently. This polycondensation reaction is carried out at 0 to 40°C, preferably 10 to 35°C.
Complete in 180 minutes, preferably 50-150 minutes.

After the reaction is completed, the desired polyester polycarbonate is obtained through a washing process consisting of water washing, pickling, water washing, alkali washing and water washing.

The polyester polycarbonate obtained by the present invention has a repeating unit represented by the following formula.

(Here, m is 2 to 15, and n is 1 to 10.) According to the method of the present invention, the desired polyester polycarbonate can be obtained through relatively simple steps. Moreover, it is a feature of the present invention that the polycarbonate units of the product can be easily adjusted. Further, in the method of the present invention, an intermediate in the production of polycarbonate can be used in the phosgenation step. Furthermore, the polyester polycarbonate obtained by the present invention has excellent thermal, mechanical and chemical properties, and is therefore extremely useful as a material for mechanical products and electrical products.

Next, the present invention will be explained in detail with reference to examples.

Example 1 15 g (0.0658 mol) of bisphenol A dissolved in 100 ml of 2N aqueous sodium hydroxide solution, 4 g (0.0197 mol) of terephthalic acid chloride and 4 g (0.0197 mol) of isophthalic acid chloride were added.
Pour the solution dissolved in 250 ml of methylene chloride into reaction vessel 1 with a baffle plate, and rotate at 400 r.p.
The reaction was carried out with stirring at m.

After 5 minutes, stirring was stopped and a methylene chloride solution (270 g/ml) of polycarbonate oligomer (average molecular weight 700) containing terminal chloroformate groups was added to the reaction vessel.
) 110 ml (the amount such that the molar ratio of hydroxyl groups and chloroformate groups in the system is 1:1), 0.15 g of paratertiary butylphenol and 0.3 ml of a 0.5 mol/aqueous triethylamine solution were added, and the rotation speed was 500 r.p.
The reaction was carried out for 50 minutes while stirring at m.

After the reaction was completed, the reaction mixture was diluted with 1 part of methylene chloride, and then 1.5 parts of water was added and stirred. Next, after separating and removing the aqueous phase, washing was performed in the order of hydrochloric acid, water, aqueous sodium hydroxide solution, and water. Thereafter, the organic phase was concentrated and purified by reprecipitation using acetone to obtain a polyester polycarbonate powder.

The reduced viscosity (ηsp/c) of this product is 0.72 (20℃,
methylene chloride), the glass transition temperature was 162°C.
The ratio of bisphenol A residue:phthalic acid residue:carbonate bond in the copolymer was 1:0.21:0.79. Here, the glass transition temperature was determined by differential thermal analysis, and the composition was determined by infrared spectrum analysis.

Example 2 15 g (0.0658 mol) of bisphenol A dissolved in 100 ml of 2N aqueous sodium hydroxide solution, 6 g (0.0296 mol) of terephthalic acid chloride and 6 g (0.0296 mol) of isophthalic acid chloride were added.
The solution dissolved in 250 ml of methylene chloride was charged into a reaction vessel 1 equipped with a baffle plate, and 0.3 ml of a 0.5 mol 1 aqueous triethylamine solution was added thereto, and the reaction was carried out with stirring at a rotational speed of 400 rpm.

After 5 minutes, stirring was stopped and a methylene chloride solution (concentration: 270
g/) 110 ml, a predetermined amount of a solution of 4.2 g of bisphenol A dissolved in 20 ml of 2N sodium hydroxide (amount such that the molar ratio of hydroxyl groups and chloroformate groups in the system is 1:1), and paratertiary 0.1 g of butylphenol and 0.3 ml of a 0.5 mole triethylamine aqueous solution were added, and the reaction was carried out for 50 minutes while stirring at a rotational speed of 500 rpm.

After the reaction was completed, the reaction mixture was diluted with 1 part of methylene chloride, and then 1.5 parts of water was added and stirred. After separating and removing the aqueous phase, the mixture was washed with hydrochloric acid, water, an aqueous sodium hydroxide solution, and water in this order. Thereafter, the organic phase was concentrated and purified by reprecipitation using acetone to obtain a polyester polycarbonate powder. The reduced viscosity (ηsp/c) of this material is 0.70 (20
℃, methylene chloride), and the glass transition temperature was 168℃. In addition, bisphenol A residues in the copolymer:
Phthalate residue:carbonate bond is 1:0.30:
It was 0.70.

Claims (1)

[Claims] 1. An alkaline aqueous solution of dihydric phenol, a saturated aliphatic dibasic acid, a halogen-substituted aliphatic dibasic acid, an aliphatic dibasic acid containing a heteroatom in the fatty chain,
Polymerization by mixing with an organic solvent solution of an acid chloride of an acid selected from the group consisting of unsaturated aliphatic dibasic acids, aromatic dicarboxylic acids, aliphatic substituted aromatic dicarboxylic acids, and polycyclic aromatic dicarboxylic acids. A polyester polycarbonate characterized in that a polyester oligomer containing hydroxyl groups with a degree of polymerization of 2 to 10 is prepared, and then a chloroformate group-containing polycarbonate oligomer with a degree of polymerization of 2 to 15 obtained from dihydric phenol and phosgene is added to perform polycondensation. manufacturing method.