JPS62148523A - Production of thermoplastic aromatic polyether aromatic polyketone - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having improved heat, chemical and hydrolytic resistance, by reacting a monomer mixture of a specific dihalogenobenzophenone derivative with a dihydroxydiphenyl derivative in the presence of sodium carbonate in a polar solvent. CONSTITUTION:A monomer mixture consisting of at least one dihalogenobenzophenone derivative expressed by formula I (X and X' are halogen; W and W' are H, 1-5C alkyl or phenyl) and at least one dihydroxydiphenyl derivative expressed by formula II (Y, Y', Z and Z' are H, 1-5C alkyl, 1-4C alkoxy, phenyl or halogen) in equimolar amounts is reacted in the presence of 1.00-1.20mol, based on 1mol monomer mixture, sodium carbonate in a polar solvent to afford the aimed polymer consisting of repeating units expressed by the formula III.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides 11u (thermal resistance, chemical resistance,
A method for producing crushed thermoplastic aromatic polyethers and aromatic polyketones without causing gelation during the reaction process.

<Prior art> A method of reacting an aromatic compound having two hydroxyl groups with an aromatic compound having two halogen atoms in the presence of potassium carbonate in a polar solvent is known (Japanese Patent Publication No. 47-21595). Publication No.).

Further, an aromatic compound having two hydroxyl groups,
A method using a mixture of potassium carbonate and sodium carbonate in polycondensation with an aromatic compound having two halogen atoms is also known (Japanese Unexamined Patent Publication No. 53-97094).
.

<Problems to be solved by the invention> In polymerization by aromatic nucleophilic substitution reaction, a phenoxy anion is produced as an intermediate, but a highly reactive potassium ion is generally used as the counter cation of this anion. It will be done. In other words,
This is the technology described in Publication No. 1595, but in this case,
When a potassium carbonate catalyst is applied to the polycondensation of a dihalogenobenzophenone derivative and a dihydroxydiphenyl derivative, it has the drawback of generating a gel-like substance.On the other hand, in the case of a mixed catalyst in which potassium carbonate and sodium carbonate are mixed, usually 1 mole of sodium carbonate is used. About 1 mol of the mixed catalyst is used, but in this case as well, the resulting polymer gels, making it difficult to obtain a useful thermoplastic resin.

The inventors of the present invention have made extensive studies to solve the above-mentioned drawbacks, and as a result, have discovered the present invention.

Means for Solving the Problems> That is, the present invention provides at least one dihalogenobenzophenone derivative represented by the following formula (I) and a compound represented by the following formula (
A thermoplastic aromatic compound consisting of repeating units @) characterized in that a mixture of essentially equimolar amounts of at least one dihydroxydiphenyl derivative of II) is reacted in a polar solvent in the presence of sodium carbonate. Method for producing polyether aromatic polyketone Z Z' (I) (n) (X1X' is a halogen atom, Y%Y', z, and z' are each independently a hydrogen atom, an alkylene group having 1 to 5 carbon atoms, μ group,
Represents an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom. w1W' each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group)
It is.

The dihalogenobenzophenone derivatives used in the present invention include 4.4'-dichlorobenzophenone, 4.4'
-difluorobenzophenone, 2,4'-dichlorobenzophenone, 2-methyl-4,4'-dichlorobenzophenone, etc., especially 4,4'-dichlorobenzophenone/:/, 4,4'-difluorobenzophenone. preferable.

The dihydroxydiphenyl derivatives used in the present invention include 4.4'-dihydroxydiphenyl A/, 3.3'
-dihydroxydiphenyl, 2゜2'-dihydroxydiphenyl #, 2-chloro-4,4'-dihydroxydiphenyl, 3-methyl-4,4'-dihydroxydiphenyl p13-methoxy-4,47-dihydroxydipheny p
However, 4,4'-dihydroxydiphenyl and 2,2'-dihydroxydiphenyl are particularly preferred.

As the polar solvent used in the present invention, DMS O
(dimethyl nurphoxite), sulfolane (tetrahydrothiophene 1,1-dioxide), dipheni/L/nurfone, NMP (N-methylhyloriton), HMPT (
Hexamethylphrephosphoric triamide), etc. Since the aromatic polyether aromatic polyketone obtained by the present invention has a high melting point and is highly crystalline, the polymer tends to precipitate as the polymerization progresses and the degree of polymerization increases. Once precipitated, the degree of polymerization cannot be increased any further, so it is ultimately necessary to carry out polymerization at a reaction temperature that is at or above the melting point of the polymer. Therefore, the polar solvent must be selected depending on the melting point of the polymer. Among them, diphenylsulfone has a boiling point of 380°C, so it can be said to be suitable for any combination of chemicals.

In the production method of the present invention, it is necessary to completely unsubstitute the inside of the reaction vessel before heating and stirring the raw material mixture. This is because the phenoxy anion generated as an intermediate during the polymerization reaction is sensitive to oxygen and is easily oxidized. If it is not substituted, the color tone will be worse than when it is not substituted, and in severe cases, the molar ratio of the monomers will shift and the degree of polymerization will not increase.

In the present invention, the molar ratio of the dihydroxydiphenyl derivative and the dihalogenobenzophenone derivative is strictly controlled.
When the ratio is 1 to 1, the degree of polymerization becomes the most extreme. Therefore, in order to obtain a polymer with a high degree of polymerization, the ratio of 1 to 1 is preferable, but in order to adjust the molecular weight, a slight excess of either raw material may be used. In this case, the excess member is b mol%
The following is preferable, and 3 mol% or less is particularly preferable. Also,
Since it is more thermally bistable if the terminal ends with a halogen than a phenol group, it is preferable to use an excess of the dihalogenobenzophenone derivative.

As a method of adjusting the molecular weight, in addition to the method of using one monomer in excess as described above (there is also a method of adding a polymerization terminator. As a polymerization terminator, at least one of the Halogenopenzenoite compounds having an electron-withdrawing group at two positions are preferred, and 4-fluorophenylntphenone, 4.4'-vchlorodiphenylspone, and 4-fluorobenzophenone are particularly preferred.

In carrying out the present invention, the amount of sodium carbonate used as a condensing agent is an important value, but theoretically, the minimum amount of carbonate required for complete exchange of all dihydroxydiphenyl derivatives to phenoxy anions. Sodium should be present.

Therefore, it is sufficient that the molar ratio of IJium carbonate and the monomer is substantially 1:1. However, in reality, the purity of sodium carbonate and sodium carbonate is not 100%, and the decomposition of phenoxy anions occurs, so the theoretical l
In contrast, the degree of polymerization may not increase in some cases.

Therefore, in order to obtain a polymer with a large molecular weight, it is necessary to carry out polymerization while changing the molar ratio of sodium carbonate and sodium carbonate to determine the optimum molar ratio.

In the present invention, the sodium carbonate/monomer ratio is LOO
Must be in the range -120.

The sodium carbonate/monomer ratio is 100 or less, for example, when sodium carbonate and potassium carbonate are mixed and the total sum is 1.
If it is set to 00, gelation may occur or the degree of polymerization will not increase sufficiently, and if it exceeds 1.20, the polymerization angle γ will increase, making it difficult for polymerization to proceed.

<Example> The present invention will be specifically described below with reference to Examples.

Example 1 4,4'-dichlorobenzophe Z725.1 was placed in a polymerization reaction vessel equipped with a helical ribbon stirring blade and a wire introduction tube.
1g (0.10mol.), 4.4'-dihydroxydiphenyl 18.62g (0.10mol.)
, anhydrous sodium carbonate IL with a particle size of 300 μm or less
O 2 g (0.104 mo1.) and 60 g of diphenylsulfone were charged, and the inside of the reaction vessel was left unsubstituted. The reaction vessel was heated to 180° C. under a nitrogen gas flow and slowly stirred. Rewarm for 30 minutes, L5 hours 250~
The temperature was maintained at 270°C. The temperature continued to rise further, and when the temperature reached 380° C. over about 2 hours, stirring was stopped and the mixture was cooled. When cooled, the reaction product solidified, so it was taken out and pulverized to form a powder of 300 μm or less.

Diphenylsulfone was removed by extracting and washing this with 300 m6 of acetone. This was followed by washing with copious amounts of water to remove inorganic salts and drying in vacuo at 120° C. overnight. This polymer of repeating units was prepared in concentrated sulfuric acid at 0.5%. sg
/dA' concentration, intrinsic viscosity measured at 25°C [η) in
h is LO9 and press molded at 450°C 7L
/mu was strong. Also, Perkin-E1mer
The melting point measured by a differential scanning calorimeter DSC-IH manufactured by Toyo Baldwin Co., Ltd. is 387°C, and the glass transition temperature obtained from the temperature dependence curve of dynamic viscoelasticity measured by Rheovipron DDV-I[-EA manufactured by Toyo Baldwin Company is The temperature was 175°C.

Example 2 25.76 g of 4.47-cyclopenzophenone (
Polymerization was carried out in the same manner as in Example 1, except that 'O, 103 mol, ) (3 motv% oversting) was used.

The intrinsic viscosity (η) inh measured in concentrated sulfuric acid at a concentration of 0.5 g/dl at 25°C was 0.83, and the film press-formed at 450°C was strong.

Example 3 Polymerization was carried out in the same manner as in Example 1, except that 3 g of 4,4'-difluorobenzophenone was added at the end of the reaction and the reaction was stopped by stirring for 30 minutes.

The intrinsic viscosity (η) inh measured in concentrated sulfuric acid at a concentration of 0.5 g/di at 25° C. was 0.8 I, and the film obtained by press molding at 450° C. was strong.

Example 4 Sulfolane (tetrahydrothiophene) was used instead of diphenyls/lephon as a polar solvent.

Polymerization was carried out in the same manner as in Example 1, except that 60 g of 1-dioxide was used. Due to the low boiling point of sulfolane, the reaction temperature was up to 280°C. 0.5g in concentrated sulfuric acid
/di concentration, intrinsic viscosity (+) measured at 25°C) inh
was O,l 8, and the film obtained by press molding at 450°C was very brittle.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that 14.37 g (0.104 mol) of potassium carbonate was used as a condensing agent instead of sodium carbonate. At the end of the polymerization, the viscosity increased, but a gel-like substance that did not dissolve in concentrated sulfuric acid was formed, so the viscosity could not be measured. In addition, we tried to obtain a film by press molding at 450°C, but the melt viscosity was high.
``A uniform sample could not be obtained.

Comparative Example 2 26.76 g of 4.4'-dichloropenzophenone (
Polymerization was carried out in the same manner as in Example 1, except that 7 mot% excess) was used. In concentrated sulfuric acid, 0
．． Intrinsic viscosity [η) measured at 25°C at 5g/di concentration
inh was 0.30. The film obtained by press molding at 450°C was brittle. [Effects of the Invention] By using the production method of the present invention, it is possible to obtain a thermoplastic aromatic polyether aromatic polyketone with less gel-like substances. can.

Claims (1)

[Scope of Claims] A monomer mixture of at least one dihalogenobenzophenone derivative represented by the following formula (I) and at least one dihydroxydiphenyl derivative represented by the following formula (II) in substantially equimolar amounts. is reacted in a polar solvent in the presence of 1.00 to 1.20 mol of sodium carbonate per mol of the monomer mixture (
III) A method for producing a thermoplastic aromatic polyether aromatic polyketone comprising: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (X, X' are halogen atoms, Y, Y', Z, and Z' each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom.W and W' each independently represent (represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a phenyl group).