JP3032072B2 - Method for producing aromatic polyether oligomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing an aromatic polyether oligomer, and more particularly to a method for producing an aromatic polyether oligomer much more easily than existing aromatic polyethers.

[0002]

2. Description of the Related Art Aromatic polyethers such as polysulfone, polyetherketone, and polyetherimide have a high secondary transition temperature (Tg) and excellent heat resistance, and can be applied to fibers, films, resins, and the like. Are being considered. Oligomers having such a polyether skeleton are useful as modifiers for various reaction molding resins and the like, and various production methods have been proposed. In addition, such an oligomer is generally a compound having a halogen derivative and a hydroxyl group, and / or
Alternatively, it is produced from a compound having various functional groups, but has many reaction steps.

[0003]

Accordingly, the present inventors have very easily
Alternatively, intensive studies have been made with the aim of providing a method for producing an aromatic polyether oligomer in a short time. As a result, they have found a method for producing an aromatic polyether oligomer very easily or in a short time by using an existing aromatic polyether as a reaction raw material as it is, and have reached the present invention.

[0004]

That is, the present invention provides an aromatic polyether having an ether group activated by an electron-withdrawing group in its main chain, and a basic compound acting as a nucleophile .
Alkali metal hydroxide, alcoholate or pheno
An alkali compound or an amine compound ,
This is a method for producing an aromatic polyether oligomer, which is characterized by causing a heat reaction.

Hereinafter, the present invention will be described in detail.

In the present invention, an ether group activated by an electron-withdrawing group refers to an ether group having an electron-withdrawing group at the O- or P-position. Here, the electron withdrawing group is preferably a sulfone group (—SO ₂ —), a ketone group (—CO—), or a nitrile group (—CN).

The polyether containing an ether group having these groups at the O- or P-position in the main chain is preferably a polyether containing the following structural units (I) to (III) in the main chain.

[0008]

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Preferred examples of the aromatic polyether having such a structure are shown below.

[0010]

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Of these, those having the structure of the formula (I) are particularly preferred.

The basic compound acting as a nucleophile used in the present invention is preferably an alkali compound or an amine compound.

As the alkali compound, an alkali metal,
Preferably, hydroxides such as sodium and potassium, alcoholates and phenolates are preferred. Further, a system for forming these in a reaction system, for example, a combined system of an alkali metal carbonate and water, or an alcohol or phenol is also preferable. When the terminal is hydroxylated, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an aromatic dihydroxy such as hydroquinone or sodium or potassium salt of 2,2-bis (4-hydroxyphenyl) propane is used. Preferable examples include an alkali metal salt of a compound or a combination system of an aromatic dihydroxy compound and an alkali metal carbonate such as sodium carbonate or potassium carbonate.

As the amine compound, aliphatic, alicyclic, and aromatic mono- and polyamino compounds can be used. In particular, when the terminal is amino-grouped, it is preferable to use a diamine compound. Examples of such a diamine compound include aliphatic diamine compounds such as hexamethylenediamine and dodecamethylenediamine; aromatic-containing aliphatic diamine compounds such as xylylenediamine; 3,4′- or 4,4′-diaminodiphenyl ether; Preferred examples include aromatic diamine compounds such as' -diaminodiphenylsulfone and 4,4'-diaminodiphenylmethane.

These nucleophiles may be used alone,
Also, two or more kinds may be used in combination. The amount of the nucleophile used varies depending on the degree of polymerization of the target oligomer, but it is 1 to 100% by weight, preferably 3 to 50% by weight, more preferably 3 to 50% by weight, based on the activated ether group of the polyether. ３０30 equivalent%.

In the reaction, the aromatic polyether and the alkaline compound are heated and reacted in the absence or in the presence of a solvent. Here, the reaction solvent is a solvent in which the aromatic polyether is dissolved, and dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone, sulfolane and the like can be preferably exemplified.

The heating reaction is preferably carried out at 50 to 400 ° C. under normal pressure or under pressure, and in some cases under an inert gas such as nitrogen gas. When a solvent is not used, it is preferably carried out at a temperature equal to or higher than the melting point of the polymer. When a solvent is used, it is preferably carried out at a temperature of 100 to 200 ° C. The reaction time is about 10 minutes to 5 hours, preferably about 20 minutes to 3 hours.

According to the present invention, an aromatic polyether oligomer having an aromatic hydroxyl group at the terminal and optionally an amino group can be obtained. If necessary, a reaction with the terminal aromatic hydroxyl group can be utilized. Furthermore, it is possible to introduce a preferable functional group, for example, an aliphatic hydroxyl group, an aliphatic amino group, an aromatic amino group or the like at the terminal.

For example, as a method for introducing an aliphatic hydroxyl group into a terminal, a method in which an aliphatic alcohol having a halogen in the molecule, for example, ethylene chlorohydrin, is added to the obtained oligomer in the presence of an alkali, followed by reaction. .

[0020]

According to the method of the present invention, very easily,
Alternatively, it becomes possible to produce an aromatic polyether oligomer in a short time.

[0021]

The present invention will be further described below with reference to examples. In the examples, "parts" means "parts by weight",
The intrinsic viscosity is phenol, tetrachloroethane 60
The measurement was carried out at a temperature of 35 ° C. using a mixed solution of 40 to 40 (weight ratio).

[0022]

Example 1 100 parts of commercially available polyether sulfone (Udel manufactured by Union Carbide), sodium hydroxide 1
0 parts and 440 parts of dimethyl sulfoxide were put into a three-necked flask equipped with a stirrer, heated to 170 ° C., and stirred for 1 hour and 30 minutes. After cooling, the precipitate was reprecipitated with methanol, washed with water and dried. The obtained polysulfone oligomer had an intrinsic viscosity of 0.22.

[0023]

Example 2 100 parts of commercially available polyether sulfone (Udel manufactured by Union Carbide), 10 parts of hexamethylene diamine and 110 parts of dimethyl sulfoxide were put into a three-necked flask equipped with a stirrer, heated to 170 ° C., and heated at 170 ° C.
After reacting for an hour, the mixture was treated in the same manner as in Example 1 to obtain an oligomer. The resulting polysulfone oligomer has a yield of 77.
Parts, intrinsic viscosity 0.28, terminal amino group concentration 136eq / t
Met.

[0024]

Example 3 Commercially available polyetheretherketone (IC
When 100 parts of PEEK (manufactured by Company I) and 11 parts of potassium hydroxide were heated to 370 ° C. in a nitrogen stream and reacted for 30 minutes, an oligomer having an intrinsic viscosity of 0.18 was obtained.

[0025]

Examples 4 to 6 100 parts of commercially available polyether sulfone (intrinsic viscosity 0.54), 800 parts of dimethyl sulfoxide and predetermined amounts of the nucleophilic reagents shown in Table 1 below were charged into a flask equipped with a stirrer, and heated under a nitrogen stream. Then, the mixture was reacted at 170 ° C. for 1 hour. After cooling, the reaction product was reprecipitated with methanol and dried. Table 1 shows the intrinsic viscosity of the obtained polysulfone oligomer.

[0026]

[Table 1]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-30527 (JP, A) JP-A-3-41120 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 65/00-65/48 C08G 73/00-73/26 C08G 75/00-75/32

Claims (1)

(57) [Claims] 1. An aromatic polyether containing an ether group activated by an electron-withdrawing group in its main chain, and a basic compound acting as a nucleophile, comprising an alkali metal hydroxide.
, Alkali which is alcoholate or phenolate
A method for producing an aromatic polyether oligomer, comprising reacting a compound or an amine compound with heat.