JPH03287625A - Ether copolymer and its manufacturing method - Google Patents

Abstract

PURPOSE:To obtain a crystalline ether copolymer excellent in heat resistance, solvent resistance and mechanical strengths by selecting an ether copolymer comprising a plurality of specified repeating units and having a specified reduced viscosity. CONSTITUTION:An ether copolymer having repeating units of formulas I and II (wherein Ar is a group of any one of formulas III-XI) in a molar compositional ratio {I/(I+II)} of 0.60-0.90 and having a reduced viscosity of 0.3dl/g or above as measured in the p-chlorophenol solution in a concentration of 0.2g/dl at 60 deg.C is selected.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ether copolymer suitably used as a material for parts in the fields of machinery, electric/electronic equipment, OA equipment, etc., and a method for producing the same.

shows. 2. The method for producing an ether copolymer according to claim 1, characterized in that the specific dihydric phenol represented by ) is reacted in a neutral polar solvent in the presence of an alkali metal compound.

3. Detailed Description of the Invention [Prior Art] In recent years, crystalline polyether has been known as a resin with excellent heat resistance, solvent resistance, and mechanical strength, and is used as an engineering resin, for example, in the automobile field and the electric/electronic equipment field. It is used in a wide range of fields such as precision machinery, OA equipment, and communication equipment. With the expansion of such fields of application, the required properties for these materials are becoming more severe, and the development of polymers with even better performance is desired.

In order to meet these demands, various proposals have been made regarding crystalline polyethers, but one with a sufficiently high glass transition temperature has not yet been obtained. For example, in Japanese Patent Application Laid-Open No. 54-90296, 4CO@O)0→
Polyethers having repeating units represented by - have been proposed. However, these polyethers have a glass transition temperature of about 143°C, which is not sufficient.

as well as [Problem to be solved by the invention] The present invention has been made in view of the above circumstances.

An object of the present invention is to provide an ether copolymer having a novel repeating unit that is crystalline and has excellent heat resistance, solvent resistance, and mechanical strength, and also to provide a suitable method for producing the same. It is.

(Means for Solving the Problems) As a result of intensive research by the present inventors to solve the above-mentioned problems, the present inventors have found that the objects can be achieved by an ether copolymer having a specific structure and reduced viscosity. The present invention was completed based on this finding.

That is, the present invention represents the following general formula. ) is expressed as its composition ratio ((1
)/((1)+(n))l is a molar ratio of 0.60 to 0.
Provided is an ether copolymer having a ratio of 90 and having a reduced viscosity of 0.3 a/g or more at 60°C in a solution with a concentration of 0.2 g/a using p-chlorophenol as a solvent. It is.

One of the important points about the ether copolymer of the present invention is that P
- The reduced viscosity at 60°C of a solution using chlorophenol as a solvent and having a concentration of 0°2 g/a is 0.3 d/g or more. If the reduced viscosity is less than 0.3 a/g, heat resistance and mechanical strength will be insufficient.

The reduced viscosity is preferably 0.8 to 2.0d17g.

In addition, the composition ratio of the copolymer ((1)/((1) +(I
f))) is 0.60 to 0.90 in molar ratio.

If the composition ratio is less than 0.60, the product will be inferior, and the heat resistance, solvent resistance, and chemical resistance will be insufficient. In addition, the composition ratio is 0.9
If it exceeds 0, the glass transition temperature will decrease and the melting point will be too high, making molding difficult.

The ether copolymer of the present invention can be used, for example, with bis(4-halogenobenzoyl)naphthalene, biphenol, and the following general formula % [[) (However, ^r in the formula is the same as in the above formula (II). be.

) can be produced by reacting the specific dihydric phenol represented by () in a neutral polar solvent in the presence of an alkali metal compound.

As bis(4-halogenobenzoyl)naphthalene,
For example, 2,6-bis(4-halogenobenzoyl)naphthalene, 2,7-bis(4-halogenobenzoyl)naphthalene, 1,5-bis(4-halogenobenzoyl)naphthalene, 1,6-bis(4-halogenobenzoyl)naphthalene, Examples include benzoyl) naphthalene. Here, the halogen is preferably chlorine or fluorine.

Of the dihydric phenol represented by formula (III),
The alkali metal compound used in the reaction may be any compound that forms an alkali metal salt of dihydric phenol.

For example, alkali metal carbonates and hydrogen carbonates are preferably used. Particularly preferably used compounds include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

Note that these may be used alone or in combination of two or more, if necessary.

Examples of the neutral polar solvent include N,N-dimethylformamide, NN-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, diethylsulfoxide, and sulfolane. , N,N-dimethylimidazolidinone, diphenylsulfone, etc. are used.

Note that these solvents may be used alone, or
If necessary, two or more types may be used. Further, if necessary, it can be used as a mixed solvent with other solvents such as aromatic hydrocarbon solvents.

The total number of moles of bis(4-halogenobenzoyl)naphthalene used in the reaction is 0.98 to 1 per mole of the total of biphenol and dihydric phenol represented by formula [■].
．． It is preferable to set the amount to 0.02 mol.

Among the alkali metal compounds, the alkali metal carbonate is preferably used in an amount of 1.02 to 1.50 mol per 1 mol of the total of biphenol and dihydric phenol represented by the formula (I[[).

Among the alkali metal compounds, the alkali metal hydrogen carbonate is 2.04 to 3.0 per mole of the total of the biphenol and dihydric phenol represented by the formula (I[[)].
Preferably, it is expressed in moles.

The ether copolymer of the present invention contains the bis(4-halogenobenzoyl)naphthalene, biphenol, the dihydric phenol represented by the formula [■], the alkali metal compound, and the neutral polar solvent in the predetermined proportions. It can be synthesized by mixing and reacting under conditions such as appropriate temperature. These raw materials may be added simultaneously or in stages. During this reaction, desired additives such as a suitable molecular weight regulator and terminal stopper can be added in appropriate amounts at appropriate stages.

The reaction temperature is preferably 180 to 380°C. reaction temperature is 1
Below 80°C, the reaction rate is too slow to be practical;
There is a risk that the produced polymer will precipitate. Also, 380°
If it exceeds C, there is a possibility that the produced polymer will be easily decomposed. The reaction time is preferably 0.5 to 5 hours, and the reaction pressure is arbitrary, but is preferably around normal pressure. The monomer concentration is 5% of the copolymer produced per 12% of the solvent.
Preferably, the concentration corresponds to 0 to 400 g.

After the completion of the reaction, there are no particular restrictions on the method of separating, recovering, and purifying the copolymer produced from the obtained polymerization solution.
Various methods used in the production of known polyethers can be used.

The ether copolymer of the present invention obtained as described above is crystalline and has a glass transition temperature of 180 to 250°.
The C1 thermal decomposition start temperature is 500 to 570°C, and has good thermal stability and excellent heat resistance.

It also has excellent solvent resistance. Furthermore, it has a high modulus of elasticity, a sufficiently large elongation, and excellent mechanical strength.

[Examples] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Example 1 Internal volume 300 equipped with stirring device and argon gas blowing pipe
- In a reactor, 22.564 g (0.06 mol) of 2.6-bis(4-fluorobenzoyl)naphthalene, 5.7 g (0.018 mol) of phenolphthalein, 4.4
'-Biphenol 7,82 g (0,042 mol), potassium carbonate 9.95 g (0,072 mol) and diphenyl sulfone 200 g were added and heated at 200°C for 30 minutes and at 340°C for 30 minutes while blowing argon gas. Made it react.

After the reaction was completed, the product was pulverized using a blender (manufactured by Warning Co., Ltd.), washed with acetone, water, and acetone in this order, and then dried to obtain 38.7 g of a powdery copolymer. The yield was 100%.

When the infrared absorption spectrum of this copolymer was measured, the chart shown in FIG. 1 was obtained.

From this result and the elemental analysis results, this copolymer was confirmed to be composed of the following repeating units.

When the properties of this ether copolymer were measured, it was found that the concentration was 0.2 g #j using P-chlorophenol as a solvent.
The reduced viscosity of the solution at 60″C is 1°41 de/g
The glass transition temperature was 215°C, the melting point was 367°C, and the thermal decomposition onset temperature was 536°C (5% weight loss in air).

In addition, a press film was prepared at 400°C, and when the film was exposed to a lighter's flame for 10 seconds to test its flame retardancy and then the flame was removed, the flame disappeared immediately and there was no melt dripping.

In addition, regarding test pieces injection molded with this copolymer, A
The mechanical strength measured according to STM D-638 was as follows.

Tensile strength 890kg/cll Tensile modulus 2
B, 000kg/cil elongation 80% Also, when the solvent resistance was investigated using the same test piece,
Acetone, chloroform, carbon tetrachloride, methylene chloride,
It was not affected by ethanol, toluene, or xylene.

Example 2 Internal volume 300 equipped with stirring device and argon gas blowing pipe
22.34 g (0.06 mol) of 2.6-bis(4-fluorobenzoyl)naphthalene was placed in a reactor of 4.af.
4'-dihydroxytetraphenylmethane 6.344g
(0,018 mol), 4,4'-biphenol 7.82
g (0,042 mol), potassium carbonate 9.95 g (
0,072 mol) and 200 g of diphenyl sulfone were added, and the mixture was reacted at 200°C for 30 minutes and at 350°C for 30 minutes while blowing argon gas.

After the reaction was completed, the product was pulverized using a blender (manufactured by Warning Co., Ltd.), washed with acetone, water, and acetone in this order, and then dried to obtain 1 g of powdered copolymer 34.

The yield was 100%.

From the results of infrared absorption spectrum measurement and elemental analysis of this copolymer, it was confirmed that this copolymer was composed of the following repeating units.

When the properties of this ether copolymer were measured, the concentration was 0.2 g/a using P-chlorophenol as a solvent.
The reduced viscosity of the solution at 60°C is 1°22 dl/g,
The glass transition temperature was 194°C, the melting point was 373°C, and the thermal decomposition onset temperature was 556°C (5% weight loss in air).

In addition, a press film was prepared at 400'C, and when the film was exposed to a lighter's flame for 10 seconds to check flame retardancy and then the flame was removed, the flame disappeared immediately and there was no melting and dripping.

In addition, regarding test pieces injection molded with this copolymer, A
The mechanical strength measured according to STM D-638 was as follows.

Tensile strength 900kg/C111 tensile modulus
31.0001cg/cta elongation 90% Also, when the solvent resistance was investigated using the same test piece,
Acetone, chloroform, carbon tetrachloride, methylene chloride,
It was not affected by ethanol, toluene, or quince.

Example 3 4.4'-dihydroxytetraphenylmethane and 44'
- An ether copolymer consisting of the following repeating units was obtained in the same manner as in Example 2, except that the molar ratio of the former to the latter was 426.

When measuring the properties of the second ether copolymer, it was found that the concentration of p-chlorophenol in each section was 0.2 g/
The reduced viscosity of the solution of di at 60'C is 1°54 dl.
/g, glass transition temperature 202°C, melting point 352°C, and thermal decomposition onset temperature 55B'C (5% weight loss in air).

Moreover, the mechanical strength of this copolymer was as follows.

Tensile strength: 880 kg/ctll Tensile modulus: 27,000 kg/cia Elongation: 60% The measurement results for flame retardancy and solvent resistance were the same as in Example 2.

Example 4 4.4′-dihydroxytetraphenylmethane and 4.4
An ether copolymer consisting of the following repeating units was obtained in the same manner as in Example 2, except that the molar ratio of the former to the latter was 25 to 5.

Elongation: 80% Furthermore, the measurement results regarding flame retardancy and solvent resistance were the same as in Example 2.

〔Effect of the invention〕

According to the present invention, it is possible to provide a crystalline ether copolymer having a novel repeating unit and excellent heat resistance, solvent resistance, and mechanical strength, and a suitable method for producing the same.

When the properties of this ether copolymer were measured, the concentration was 0.2 g/d using p-chlorophenol as a solvent.
The reduced viscosity of the solution of 1 at 60°C is 1°32 dl/
g, glass transition temperature 191°C, melting point 378°C1 thermal decomposition onset temperature 561°C (5% weight loss in air).

Moreover, the mechanical strength of this copolymer was as follows.

Tensile strength 910kg/cd Tensile modulus 31,000kg/d

[Brief explanation of drawings]

FIG. 1 is a chart showing the infrared absorption spectrum of the ether copolymer obtained in Example 1 of the present invention. The horizontal axis of the figure shows the wave number (am-'), and the vertical axis shows the absorption intensity.

Claims (1)

[Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, Ar in the formula is ▲ mathematical formula, There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates. ) is the repeating unit represented by its composition ratio {[
I]/([I]+[II])} is a molar ratio of 0.60 to 0
．． An ether copolymer having a ratio of 90 and having a reduced viscosity of 0.3 dl/g or more at 60°C in a solution having a concentration of 0.2 g/dl using p-chlorophenol as a solvent. 2. Bis(4-halogenobenzoyl)naphthalene, biphenol, and the following general formula HO-Ar-OH [III] (However, Ar in the formula has ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula, a table, etc.) There are ▼, ▲mathematical formula, chemical formula, etc.
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates. 2. The method for producing an ether copolymer according to claim 1, characterized in that the specific dihydric phenol represented by ) is reacted in a neutral polar solvent in the presence of an alkali metal compound.