JPH0446930A - Preparation of polyether copolymer - Google Patents

Abstract

PURPOSE:To prepare the title copolymer having a high mol.wt., a crystallizability, an excellent heat resistance, and high mechanical strengths at a high productivity by copolymerizing three raw materials in a specified ratio in two steps, each step being conducted in a specified temp. range. CONSTITUTION:The title copolymer is prepd. by copolymerizing 0.15-0.40mol of a dihalogenobenzonitrile, 0.85-0.60mol of a 4,4'-dihalogenobenzophenone (the sum of these two reactants being 1.0mol), and substantially 1.0mol of 4,4'- biphenol in two steps, the first step at 220-260 deg.C and the second step at 310-350 deg.C. The polyether, having a crystallizability and sufficient resistance to heat and solvent as well as excellent mechanical strengths, is useful as a material in the fields of, e.g., electric and electronic apparatuses and machinery.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a polyether copolymer, and more specifically, it has crystallinity and exhibits sufficient heat resistance, as well as solvent resistance. The present invention relates to a method for producing with good productivity a polyether copolymer which has excellent mechanical strength and is useful as a material in, for example, the electrical/electronic equipment field, the mechanical field, etc.

[Issue 8 to be solved by the prior art and the invention] In recent years,
Engineering resins with various structures have been developed and are used in a wide range of fields such as automobiles, electrical and electronics, precision machinery, OA equipment, and optical communication equipment, but their performance is However, the required performance has not yet been fully satisfied, and the required performance has become stricter, so the development of new materials is desired.

On the other hand, one of these engineering resins is a certain polyether copolymer, which has particularly excellent heat resistance.
Various proposals have also been made regarding this polyether copolymer.

For example, in Japanese Patent Application Laid-open No. 47-14270,
A method for producing an aromatic polyether copolymer has been proposed in which dinitrobenzonitrile, dihalogenobenzophenone, and dihydric phenol are reacted in the presence of an alkali metal compound.

However, according to this conventional method, only a low molecular weight copolymer with a melt viscosity of 200 voids or less at 400°C can be obtained, and the resulting copolymer does not have sufficient heat resistance or mechanical strength. It is hard to say that it is practical.

Furthermore, in JP-A No. 60-235835, the following formula (a); and a repeating unit represented by the following formula (b) (however, Ar in the above formula is a divalent aromatic group), and a repeating unit represented by the above formula (a). Composition ratio of units (molar ratio; (a)/[(a) + (b)
] ) is 0.5 or more, a method for producing a polyether copolymer has been proposed.

However, a polyether copolymer in which the composition ratio of repeating units represented by formula (a) is 0.5 or more,
Since it is amorphous, it cannot maintain mechanical strength in a temperature range exceeding the glass transition temperature, and it is difficult to say that it has sufficient heat resistance.

On the other hand, in this conventional method, if the raw material mixture corresponding to a copolymer having a repeating unit composition ratio of the formula (a) is less than 0.5 is immediately subjected to a copolymerization reaction at a high temperature, it is insufficient. It is not possible to obtain a high molecular weight polyether copolymer.

The present invention has been made based on the above circumstances.

The purpose of the present invention is to produce a polyether copolymer that has crystallinity, exhibits extremely excellent heat resistance, has a sufficiently high molecular weight, has excellent mechanical strength, etc., and is useful as a new material, in a specific proportion. It is an object of the present invention to provide a method for producing with high productivity by carrying out a two-step copolymerization reaction of raw materials in a specific temperature range.

[Means for Solving the Problems] In order to achieve the above object, the structure of the present invention is such that o, is an amount of dihalogenobenzonitrile corresponding to ~0.4 and an amount of 4.4 corresponding to a molar ratio of 0.85 to 0.6 with respect to the total amount
The first stage copolymerization reaction of °-dihalogenobenzophenone and 4.4°-biphenol in an amount substantially equimolar to the above total amount is carried out at 220 to 260°C in the presence of an alkali metal compound and diphenyl sulfone. carried out in the temperature range of
This is a method for producing a polyether copolymer, characterized in that the second stage copolymerization reaction is carried out in a temperature range of 310 to 350°C.

In the method of the present invention, specific examples of the dihalogenobenzonitrile used include the following formula.

(In the formula, X is a halogen atom.) 2,6-dihalogenobenzonitrile or the formula.

Examples include 2,4-dihalogenobenzonitrile represented by the following formula (in the formula 1, X has the same meaning as above).

Among these, preferred are 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2.4-dichlorobenzonitrile.
-dichlorobenzonitrile, 2,4-difluorobenzonitrile, and particularly preferred is 2,6-dichlorobenzonitrile.

In addition, in the method of the present invention, the above-mentioned 4,
4°-dihalogenobenzophenone has the following formula; (however,
X has the same meaning as above. ), and in the method of the present invention, 4.4°-difluorobenzophenone and 4,4°-dichlorobenzophenone can be particularly preferably used.

Furthermore, the 4,4°-biphenol is a compound represented by the following linear formula:

The alkali metal compound used in the method of the present invention is not particularly limited as long as it can convert the 4.4°-biphenol into an alkali metal salt, but
Preferred are alkali metal carbonates and alkali metal hydrogen carbonates.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

In the method of the present invention, among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used.

In the method of the present invention, the proportion of the dihalogenobenzonitrile used in the copolymerization reaction is from 0.15 to 0.15 as a molar ratio to the total amount of dihalogenobenzonitrile and 4.4°-dihalogenobenzophenone used. It is important to set the ratio in the range of 0.4, preferably 0.2
The ratio ranges from ~0.3.

The proportion of the 4,4°-dihalogenobenzophenone used is preferably 0.85 to 0.6 as a molar ratio to the total amount, that is, the total amount of dihalogenobenzonitrile and 4,4°-dihalogenobenzophenone. is 0.8~0
．． The ratio is 7.

Here, if the usage ratio of the dihalogenobenzonitrile is outside the range of 0.15 to 0.4 according to the above definition (
Therefore, if the proportion of the 4,4'-dihalogenobenzophenone used is outside the above-mentioned range of 0.85 to 0.6), it will have a predetermined proportion of repeating units having the excellent properties described below. However, it is not possible to obtain a polyether copolymer with a sufficiently high molecular weight.

In the method of the present invention, the above-mentioned 4 to be subjected to the copolymerization reaction
, 4°-biphenol is used in a substantially equimolar amount based on the total amount of the dihalogenobenzonitrile and the 4,4'-dihalogenobenzophenone used.

Here, to make this ratio substantially equimolar is 4,4
Based on the theory that °-biphenol reacts with dihalogenobenzonitrile and 4.4°-dihalogenobenzophenone in an equimolar stoichiometric ratio in the copolymerization reaction, Alternatively, it is intended to convert it into a desired polyether copolymer with as little waste as possible. Therefore, the usage ratio of 4,4°-biphenol according to the above definition is not necessarily limited to this, considering the stoichiometric ratio and whether it is desirable to make it as equimolar as possible. There is no deviation, and some variation is allowed as long as it does not impair productivity.

The ratio of the alkali metal compound used is the 4,4°-
1 per hydroxyl group of biphenol 1 usually 1, old to 2.5
0 equivalents, preferably l. A suitable proportion is 0.02 to 1.20 equivalents.

In order to obtain the desired polyether copolymer by the method of the present invention, the dihalogenobenzonitrile, 4.4'
-Dihalogenobenzophenone, 4,4°-biphenol and an alkali metal compound are added to a reactor together with diphenylsulfone, and the first stage copolymerization reaction is first carried out with
Performed in a temperature range of 20 to 260°C, in which case 140 to 1
The added diphenyl sulfone is dissolved at a temperature of 60°C, and this is used as a solvent.

If the first-stage copolymerization reaction is carried out at a low temperature below 220°C, the reaction rate of the raw material is not sufficient, so the raw material is dissipated from the reaction system by evaporation or sublimation, and the halogen compound components (dihalogenobenzonitrile and 4,4゛-dihalogenobenzophenone) and 4.4
The problem arises that the molar balance of °-biphenol deviates significantly from the predetermined stoichiometric ratio, and that the increase in molecular weight does not proceed. On the other hand, the temperature of one reaction system was increased to 260°C without performing the first stage copolymerization reaction in the predetermined temperature range.
If the temperature is raised to a temperature higher than 0.degree. C., oligomers with a high melting point are produced, which causes the reaction solution to solidify, resulting in a problem that the increase in molecular weight does not proceed.

Note that the time for carrying out this first stage copolymerization reaction is usually 1,
The appropriate time is 20 minutes to 2 hours, preferably 30 to 100 minutes.

In the method of the present invention, the temperature of the product of the first stage copolymerization reaction is then raised to a temperature range of 310 to 350°C, and the second stage copolymerization reaction is carried out in that temperature range.

If this second stage copolymerization reaction is carried out in a temperature range below 310°C, the polymerization of the polymer will be inhibited due to solidification of the reaction solution. On the other hand, if the temperature of the reaction system is raised to a temperature exceeding 350° C., problems arise such as coloring of the product and formation of gel.

Note that the time for carrying out this second stage copolymerization reaction is usually
A suitable time is 10 to 60 minutes, preferably 20 to 30 minutes.

In the method of the present invention, as described above, it is important to use a specific solvent called diphenyl sulfone as a solvent in the copolymerization reaction.

The amount of diphenylsulfone used as this solvent is:
The amount of copolymer produced per 1 kg of diphenyl sulfone is usually 200 to 600. It is appropriate to determine the amount corresponding to the proportion.

As described above, by carrying out the copolymerization reaction in two stages and using diphenyl sulfone as a solvent according to the method of the present invention, the concentration of the produced copolymer in the solvent can be sufficiently increased as described above. Therefore, it is possible to smoothly increase the molecular weight, and moreover, the amount of raw material can be converted into the desired polyether copolymer without wasting it, which can significantly improve productivity. be.

When using other methods such as conventional methods, even if diphenylsulfone is used as a solvent, problems such as solidification of the reaction system may occur as described above, and precipitation of the produced copolymer may occur. This causes the problem that the molecular weight does not increase sufficiently.

1. In the method of the present invention, a mixed solvent containing diphenyl sulfone as a main component may be used by adding other appropriate solvent components together with diphenyl sulfone to the extent that it does not interfere with the purpose of the present invention. It is also possible to carry out the above copolymerization reaction.

Similarly, the above-mentioned copolymerization reaction can be carried out by adding other components or additives to one reaction system within a range that does not impede the purpose of the present invention.

For example, 1.4-
Bis(4-chlorobenzoyl)benzene, 1°4-bis(4-fluorobenzoyl)benzene, 4°4°-bis(4-chlorobenzoyl)diphenyl ether, 4.4
°-Bis(4-fluorobenzoyl)diphenyl ether, 4,4°-bis(4-chlorobenzoyl)cyphenyldioether, 4.4°-bis(4-)fluorobenzoyl)diphenylthioether, 4°4' -Bis(4-
chlorobenzoyl)biphenyl, 4゜4'-bis(4-
fluorobenzoyl) biphenyl.

4.4°-bis(4-chlorobenzoyl)diphenylmethane, 4,4°-bis(4-fluorobenzoyl)diphenylmethane, 4,4′-bis(4-chlorobenzoyl)dibenzofuran, 4.4°-bis(4 -fluorobenzoyl)dibenzofuran, 4.4°-bis(4-chlorobenzoyl)dibenzothiophene, 4.4'-bis(
4-fluorobenzoyl)dibenzothiophene.

2.6-bis(4-chlorobenzoyl)naphthalene, 2
．． 6-bis(4-fluorobenzoyl)naphthalene, 2
．． 5-bis(4-chlorobenzoyl)pyridine, 1.4
-bis(4-chlorophenylsulfonyl)benzene, 2
．． 6-bis(4-chlorophenylsulfonyl)naphthalene, 4,4゛-dichlorodiphenylsulfone, 4.4
Examples include compounds such as '-difluorodiphenylsulfone.

After completing the second stage copolymerization reaction, the polyether copolymer is separated and purified from the resulting diphenylsulfone solution containing the polyether copolymer according to a known method.

A polyether copolymer can be obtained.

According to the method of the invention.

It consists of a repeating unit represented by the following formula (I): (I) and a repeating unit represented by the following formula (■): (n), and the composition ratio [molar ratio] of the repeating unit represented by the formula (I) is :(r)/((r)
+ (II))] is 0.15 to 0.40 mol, and the melt viscosity at 400°C is: l, 000 to 10
A polyether copolymer resin having a void of 0.000 can be obtained.

It is important, as shown below, that the polyether copolymer produced by the method of the present invention has the above-mentioned specific repeating unit composition.

That is, if the composition ratio of the repeating units represented by the formula (I) is less than 0.15, the glass transition temperature of the polyether copolymer may become low, resulting in a decrease in heat resistance or a high melting point. This may lead to deterioration of moldability. On the other hand, if the composition ratio exceeds 0.4, the crystallinity of the polyether copolymer is lost, resulting in a decrease in heat resistance and solvent resistance.

Further, the polyether copolymer produced by the method of the present invention has a melt viscosity of 3.0 at a temperature of 400°C.
It is also important that the number of voices is 00 or more.

This is because it is difficult to achieve sufficient heat resistance and mechanical strength with a low molecular weight polyether copolymer having a melt viscosity of less than 3,000 voids.

The polyether copolymer having the predetermined composition ratio and melt viscosity produced by the method of the present invention has, for example, a crystal melting point of about 330 to 400°C, has crystallinity, and has sufficient polymer It exhibits sufficient heat resistance and is excellent in solvent resistance, mechanical strength, etc., and can be suitably used as a new material in, for example, the electrical/electronic equipment field and the mechanical field.

[Example] Next, the present invention will be explained in more detail by showing examples of the present invention and comparative examples thereof.

(Example 1) 4.4°-Dichlorobenzophenone: 169.27 g (1,456 mol), 2
．． 6-cyclopenzonitrile 108.41g (0,
624 mol), 4,4'-biphenol 186.9
g (2.08 mol), anhydrous potassium carbonate 345 g
(2,496-T-nyl) and diphenylsulfone 1
．． 6 kg was added, and the diphenyl sulfone was melted at a temperature of 140 to 160°C, and the above compound was dissolved.

Next, the temperature was raised to 250°C, and the first stage copolymerization reaction was carried out at the same temperature for 90 minutes.

Next, the temperature of the reaction system was raised to 340°C, and the second stage copolymerization reaction was carried out at the same temperature for 20 minutes.

After the reaction was completed, one reaction product was poured into a stainless steel vat and cooled to obtain a plate-like body.

This plate-shaped body is crushed into particles with an average particle size of 1 mm or less,
This was washed sequentially with methanol and water, dried,
712 g (yield: 100%) of a white powdery copolymer was obtained.

When infrared absorption spectrum analysis was performed on the obtained copolymer, absorption due to nitrile groups was observed at the position of 2,220 cm-', absorption due to carboxyl groups was observed at the position of 1,650 cm-', and absorption due to the carboxyl group was observed at the position of 1,240 cm-'. Absorption due to ether bond was confirmed at the ' position.

From the results of this IR analysis and the elemental analysis, it was confirmed that the copolymer obtained was a polyether copolymer consisting of repeating units having the following structure.

In addition, when the physical properties of this polyether copolymer were measured, the glass transition temperature was 184.5°C, and the crystal melting point was 35°C.
8℃, thermal decomposition start temperature is 570℃, temperature is 400℃
The melt viscosity (zero shear viscosity) was 46,000 voids, indicating that it was a polyether copolymer with high heat resistance and a sufficiently high molecular weight.

Furthermore, when the crystallinity of this polyether copolymer was measured by scattering intensity using wide-angle X-rays, the crystallinity was 46%, confirming that it had crystallinity.

An attempt was made to measure the viscosity of the solution, but due to its high solvent resistance, it did not dissolve in any organic solvent and could not be measured.

(Example 2) The same procedure as in Example 1 was carried out except that the second stage copolymerization reaction was carried out at 330°C for 90 minutes, and 712 g (yield 100%) of a white powdery copolymer was obtained. Obtained.

It was confirmed by IR analysis, elemental analysis, etc. that this copolymer was a crystalline polyether copolymer having the same repeating units and composition ratio as the copolymer obtained in Example 1.

In addition, when the physical properties of this polyether copolymer were measured, the glass transition temperature was 184.2°C, and the crystal melting point was 36.
0°C1 thermal decomposition start temperature is 570°C1 crystallinity is 45
%, and the melt viscosity (zero shear viscosity) at a temperature of 400°C was 38,000 Bois.

It should be noted that an attempt was made to measure the solution viscosity, but due to its high solvent resistance, it did not dissolve in any organic solvent and could not be measured.

(Comparative Example 1) Copolymerization was carried out in the same manner as in Example 1, except that the first stage copolymerization reaction was carried out at 210°C for 90 minutes, and then the second stage copolymerization reaction was carried out at 340°C for 20 minutes. An attempt was made to produce a polymer.

However, the copolymerization reaction product I at 210°C in the first stage
& In the process of raising the temperature of the material to 340°C, a lot of carbon dioxide gas was generated, and 91
Is it adhesion to the reactor wall due to flowers?

7.3g and 1.2g were found, respectively.

The yield of the obtained copolymer was 684 g (yield 96%)
Furthermore, the melt viscosity of this copolymer at 400° C. was as low as 2,600 voices, indicating that there was no polymer with a sufficiently high molecular weight.

The glass transition temperature of this copolymer is 180. :1℃
The melting point was 366°C.

(Comparative Example 2) An attempt was made to produce a copolymer using the same procedure as in Example 1, except that the first stage copolymerization reaction was carried out at 270°C.

However, after the first stage copolymerization reaction proceeded at 270''C for 20 minutes, the reaction system solidified and the product was an oligomer.

(Comparative Example 3) A copolymer was produced in the same manner as in Example 1 except that the second stage copolymerization reaction was carried out at 360°C for 10 minutes, and the yield was 7.
12 g (100% yield) of copolymer was obtained.

This copolymer has a glass transition temperature of 186.5°C.

Although it has a melting point of 353℃ and has high heat resistance, its melt viscosity at 400℃ is extremely high at 126,000 voids, and it has a sufficiently high molecular weight or contains a large amount of gel, and has a dark brown color. It was showing.

[Effects of the Invention] According to the present invention, a specific method is adopted in which a copolymerization reaction is carried out in two stages using a specific proportion of raw materials and in a specific temperature range in a specific solvent. In addition to being crystalline and exhibiting extremely excellent heat resistance,
It is possible to provide a method for producing a polyether copolymer having a specific composition, which has a sufficiently high molecular weight, excellent mechanical strength, etc. and is useful as a new material, in high yield and with good productivity.

Claims (1)

[Claims] (1) 0.1 molar ratio based on the total amount of dihalogenobenzonitrile and 4,4'-dihalogenobenzophenone
dihalogenobenzonitrile in an amount corresponding to 5 to 0.4, 4,4'-dihalogenobenzophenone in an amount corresponding to a molar ratio of 0.85 to 0.6 with respect to the total amount, and the total amount and 4,4'-biphenol in a substantially equimolar amount in the presence of an alkali metal compound and diphenyl sulfone in the temperature range of 220 to 260°C, and the second stage Copolymerization reaction 310-350
A method for producing a polyether copolymer, characterized in that it is carried out in a temperature range of °C.