JPH03122121A - Polyether-based copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a polyether-based copolymer having excellent heat resistance, moldability, etc., containing specific two kinds of repeating units in a specific ratio by reacting specific components such as 4,4'- dihydroxybenzophenone. CONSTITUTION:1 mol 4,4'-dihydroxybenzophenone is reacted with 0.1-0.3 mol dihalogenobenzonitrile and 0.7-0.9 mol dihalogenobenzophenone in the presence of an alkali compound in a neutral polar solvent to efficiently give a polyether copolymer suitable as an element in the field of automobile, containing a repeating unit shown by formula I and a repeating unit shown by formula II in the ratio of I/I+II=0.1-0.3, preferably 0.1-0.2 and having >=3,000 poise, preferably 10,000-30,000 poise at 400 deg.C.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel polyether copolymer and a method for producing the same. More specifically, the present invention relates to a novel polyether copolymer and a method for producing the same. It has excellent flame retardancy and mechanical strength, as well as good moldability, and is suitable for example in the automobile field, electrical/electronic field, and precision machinery field. The present invention relates to an aromatic polyether copolymer useful as a material in the field of office automation equipment or optical communication, and a method for producing the same.

[Prior art and problems to be solved by the invention] In recent years,
Engineering resins with various structures have been developed, for example in the automobile field.

Although it is used in a wide range of fields such as electrical and electronic fields, precision machinery fields, OA equipment fields, and optical communication equipment fields, its performance has not yet reached full satisfaction in all aspects. As performance has become stricter, the development of new materials is desired.

On the other hand, aromatic polyetherketone, which is one of these engineering resins, has crystallinity and is particularly excellent in heat resistance, and various proposals have been made regarding this aromatic polyetherketone.

For example, in Japanese Patent Application Laid-open No. 54-90296,
A thermoplastic aromatic polyetherketone containing a repeating unit represented by the following formula either alone or together with other repeating units and having an intrinsic viscosity of 0.7 or more is disclosed.

Moreover, in JP-A-61-138526, the following formula % formula % [However, pH in the formula is a phenylene group. It has a repeating unit A represented by a linear formula; and a repeating unit B represented by a linear formula; molar ratio [(repeat unit A) = (repeat unit B)]
95:5 to 60:40 and a melt viscosity measured at a temperature of 400° C. of 0.06 kN, S, n-1 or more is disclosed.

However, these aromatic polyetherketones have a relatively low glass transition temperature of, for example, about 143°C to 155°C, and cannot maintain rigidity in a temperature range exceeding the glass transition temperature, resulting in lIJ Heat resistance is not sufficient.

The purpose of the present invention is to provide an aromatic polyether that has improved heat resistance, excellent solvent resistance, mechanical strength, and good moldability, and a method for efficiently producing this aromatic polyether. It is about providing.

[Means for solving the problem] The invention according to claim 1 to achieve the above object is as follows:
The following formula (1): A polyether copolymer characterized by having a poise of 3,000 poise or more.

The invention according to claim 2 provides the following: 4,4'-dihydroxybenzophenone and 0.1 to 0.1 to dihalogenobenzonitrile per mole of 4,4°-dihydroxybenzophenone.
0.3 mol of 4,4°-dihalogenobenzophenone and 0.7 to 0.9 mol of 4,4°-dihalogenobenzophenone are reacted in a neutral polar solvent in the presence of an alkali metal compound. This is a method of manufacturing a combination.

The composition ratio of the repeating unit represented by the formula (I) is [CI)/((I)+(
II))] is 0.1 to 0.3, and the temperature is 40
One of the important points in the polyether copolymer according to claim 1 is that the melt viscosity at 0°C is - polyether copolymer - The composition ratio of the repeating unit represented by the formula (I) is within the range of 0.1 to 0.3.

The composition ratio of the repeating unit represented by the formula (1) is 0.
If it is less than 1, the glass transition temperature of the polyether copolymer will be low, resulting in a decrease in heat resistance, or the melting point will be high, leading to deterioration in moldability.

On the other hand, if it exceeds 0.3, the crystallinity of the polyether copolymer will be lost, resulting in decreased heat resistance, solvent resistance, and chemical resistance.

In the polyether copolymer of the present invention, the above formula (
The repeating units represented by formula (II) are added in a ratio of 0-1 to 0.3, preferably 0.1 to 0.2.
) is contained in a ratio of 0.7 to 0.9, preferably 0.8 to 0.9.

Further, the polyether copolymer of the present invention has a melt viscosity of 3,000 voids or more at a temperature of 400°C,
It is important that the range is preferably io, ooo to 30,000 voices.

A low molecular weight polyether copolymer having a melt viscosity of less than 3,000 voids cannot achieve sufficient heat resistance or solvent resistance.

-Production method of polyether copolymer- The polyether copolymer according to claim 1 can be produced according to the method according to claim 2.

As a preferable example thereof, for example, dihalogenobenzonitrile, 4,4'-dihydroxybenzophenone and 4,4'-dihydroxybenzophenone,
Examples include a method of reacting 4'-dihalogenobenzophenone in the presence of an alkali metal compound and a neutral polar solvent.

In this case, specific examples of the dihalogenobenzonitrile that can be used include 2,6-dihalogenobenzonitrile represented by the following formula; (wherein, X is a halogen atom); .

Examples include 2,4-dihalogenobenzonitrile represented by the following formula: (wherein, 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 2,6-dichlorobenzonitrile is particularly preferred.

The 4,4'-dihalogenobenzophenone to be used is a compound represented by the following formula (wherein, X has the same meaning as above), and in the present invention, 4,4'-difluorobenzophenone , 4.4°-dichlorobenzophenone, and 4-chloro-4-fluorobenzophenone can be particularly preferably used.

The alkali metal compound to be used is as described in 4.4 above.
``-Dihydroxybenzophenone can be converted into an alkali metal salt without any particular limitation, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.

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.

Among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, tomethyl-2-pyrrolidone (NMP
), N-ethyl-2-pyrrolidone, N-isopropyl-
2-pyrrolidone, N-inbutyl-2-pyrrolidone, N
-n-propyl-2-pyrrolidone, N-n-butyl-2
-pyrrolidone, N-cyclohexyl-2-pyrrolidone,
N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, tomethyl-3°4.5
-1-limethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, -methyl-6-methyl-2-piperidone, N-methyl-3- Ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-
1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N, N'
-dimethylimidazolidinone (DMI), diphenyl sulfone, and the like.

Preferred are NMP, DMI, sulfolane, and diphenylsulfone.

The usage ratio of dihalogenobenzonitrile in tj is 4.4
The ratio is 0.1 to 0.3 mol of dihalogenobenzonitrile per 1 mol of '-dihydroxybenzophenone.

Said 4. The ratio of ao-dihalogenobenzophenone used is 0.7 to 0.4,4,4'-dihalogenobenzophenone per mole of 4,4'-dihydroxybenzophenone.
The ratio is 9 moles.

The proportion of the alkali metal compound used is 4°4'-
In the case of carbonate, it is 1.05 to 1.5 mol, preferably 1.10 to 1 mol, per 1 mol of dihydroxybenzophenone.
．． 20 mol, twice that amount for hydrogen carbonate.

There is no particular restriction on the amount of the neutral polar solvent used, but usually the dihalogenobenzonitrile and the 4,4
200 to 2,00 parts per 100 parts by weight of the total of ゛-dihydroxybenzophenone and the alkali metal compound
It is selected within the range of 0 parts by weight.

In order to obtain the polyether copolymer according to claim 1 by the method of the present invention, for example, in the neutral polar solvent,
The dihalogenobenzonitrile and the 4,4°-dihydroxybenzophenone are reacted in the presence of an alkali metal compound, and the 4,4°-dihydroxybenzophenone is further added, usually at 150 to 380°C, preferably. A series of reactions are carried out in the range of 180 to 330°C.

If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur.

In addition, the reaction time of this series of reactions is usually 0.1 to 1
0 hours, preferably 1 to 5 hours.

After the reaction is completed, the polyether copolymer can be obtained by separating and purifying the polyether copolymer from the neutral polar solvent solution containing the obtained polyether copolymer according to a known method. can.

For example, after the reaction is complete, if the neutral polar solvent is still mixed in,
After powdering, the powder is washed with acetone, methanol, water, and acetone in this order, and dried to obtain a polyether copolymer.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) In a 300 m separable flask equipped with a stirring device, 10.71 g of 4,4°-dihydroxybenzophenone was added.
1 g (0.05 mol), 2.6-cyclobenzonitrile 1.72 g (0.01 mol), difluorobenzophenone 8.728 g (0.04 mol), potassium carbonate 7.256 g (o, o525-v- 7,100 g of Schiff x-Rustle* were added thereto, and the mixture was reacted at 200° C. for 1 hour while flowing argon gas.

Next, the 0 reaction product was heated and stirred at 280 °C for 30 minutes and 320 °C for 1 hour, then cooled, crushed, washed with acetone, water, and acetone in this order, and then dried. 18.5g of white powder (
A yield of 99% was obtained.

When IR measurement was performed on this white powder, it was found to be 2.22
Absorption by nitrile group at 0 cm-1 (7) position, 1.6
Absorption by carbonyl group at 50 cm-1, 1.2400
Absorption due to an ether bond was confirmed at the position of " ].

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

Further measurements of the properties of this polyether copolymer revealed that the melt viscosity (zero shear viscosity) at a temperature of 400°C was 12,000 poise, and the glass transition temperature was 171.
℃, crystal melting point is 325℃, thermal decomposition onset temperature is 560℃ (
(5% weight loss in air).

(Examples 2 to 3) In Example 1, the ratios of 2,6-cyclobenzonitrile and 4,4"-difluorobenzophenone were changed to those shown in Table 1.
It was carried out in the same manner.

The above formula (I) in the obtained polyether copolymer
: The content ratio of repeating units represented by: and the melt viscosity and thermal properties of the obtained polyether copolymer
Shown in the table.

(Comparative Examples 1 to 2) Same procedure as in Example 1 except that the proportions of 2,6-cyclobenzonitrile and 4,4"-difluorobenzophenone were changed as shown in Table 1. The results are shown in Table 1.

Table 1 [Effects of the Invention] The present invention provides a novel structure that has improved heat resistance, excellent solvent resistance, flame retardancy, and mechanical strength, and is easy to mold due to its low melting point. It is an object of the present invention to provide a method for producing a polyether copolymer that can efficiently obtain such an excellent polyether copolymer in a simple process. can.

Wood 1: Amorphous: No melting point

Claims (1)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼Contains repeating units represented by (II), and the composition ratio of the repeating units represented by formula (I) above [(I)/{(I)+(II)}] is 0.1 ~0.3, and the melt viscosity at a temperature of 400°C is 3.0
A polyether copolymer characterized by having a poise of 00 poise or more. (2) 4,4'-dihydroxybenzophenone, 0.1 to 0.3 mol of dihalogenobenzonitrile and 0.7 to 4,4'-dihalogenobenzophenone per 1 mol of 4,4'-dihydroxybenzophenone 0
．． The method for producing a polyether copolymer according to claim 1, characterized in that 9 moles of the polyether copolymer are reacted in the presence of an alkali metal compound in a neutral polar solvent.