JPS63291920A - Production of sulfonated polyaryl ether ketone - Google Patents

Abstract

PURPOSE:To obtain the titled compound having excellent characteristics with advantageous separation, recovery, etc., by bringing a polyaryl ether ketone into contact with a specific gas, such as sulfur trioxide, and carrying out sulfonation without causing excess sulfonation or reduction of molecular weight. CONSTITUTION:A polyaryl ether ketone, expressed by the formula (p is 0 or 1; Ar, Ar' and Ar'' are bifunctional aromatic group) and having preferably 0.8-2.5 reduced viscosity (measured by using a 98% sulfuric acid solution in 0.1g/dl concentration) is brought into contact with a gaseous or misty compound selected from sulfur trioxide, chlorosulfonic acid or fluorosulfonic acid to afford the aimed compound. Furthermore, the gas or mist of the compound used for the above-mentioned sulfonation is obtained by blowing an inert gas, such as air or nitrogen into a melt, solution prepared by dissolving the compound in carbon tetrachloride, hexachloroethane, etc., or fuming sulfuric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a sulfonated polyaryletherketone.

(Prior Art) Polyaryletherketone is a resin that can be processed by melt molding and has excellent thermal stability, chemical resistance, electrical properties, mechanical properties, radiation resistance, etc. As an attempt to take advantage of these characteristics and introduce functional groups into this polymer to use it for more applications, Japanese Patent Application Laid-Open Nos. 65-86296 and 57-25828 disclose A sulfonated polyaryletherketone obtained by sulfonating the aromatic nucleus of a polyaryletherketone in concentrated sulfuric acid is disclosed.

(Problems that N-Ming attempts to solve) However, the method of sulfonating polyaryletherketone in concentrated sulfuric acid has many problems as described below. In other words, as the sulfonation reaction progresses, the reaction system generates heat, and there is a high probability that most of the aromatic nuclei of the polyaryletherketone will be sulfonated; As the molecular weight of the polyaryletherketone decreases, many of the original characteristics of the polyaryletherketone are lost. Furthermore, a large amount of neutralizing alkali is required to separate and recover the target sulfonated polyaryletherketone from the sulfonation reaction mixture, and many post-processing steps such as washing and drying are required. do. Furthermore, the WK of sulfonation is difficult to control because the contact time with concentrated sulfuric acid is generally long. Furthermore, since sulfonated polyaryletherketones with a high degree of sulfonation are easily swollen by water, it is extremely difficult to recover such products from aqueous systems.

The purpose of the present invention is to easily separate and recover sulfonated polyaryletherketone from a reaction mixture without causing excessive sulfonation or molecular weight reduction of the polymer that would cause the polyaryletherketone to lose its characteristics. An object of the present invention is to provide a method for producing a sulfonated polyaryletherketone that can easily control the degree of sulfonation and can be melt-molded and has excellent properties.

(Means for Solving the Problems) The present inventor has continued research on the sulfonation of polyaryletherketones. As a result, the inventors discovered that sulfonated polyaryletherketones can be obtained very conveniently by sulfonation with a specific compound, leading to the completion of the present invention.

That is, the present invention provides a structure containing a repeating structural unit represented by the following general formula (+0-Ar÷0-Ar'-I Co -Ar"+ (
x) (where p is 0 or 1, Ar, Ar'# and A
(r' is a divalent aromatic group) A sulfonated polyester characterized by contacting a polyaryletherketone with a compound selected from the group consisting of gaseous or mist sulfur dioxide, chlorosulfonic acid, and fluorosulfonic acid. This is a method for producing aryl ether ketone.

The above general formula (as a specific example of + O-C) 0-0-co @su, +o(◇-co@
÷, + o@-C) o-Qo-co-@+ etc.
Lukoto can be done. lI containing these repeating structural units
The reduced viscosity of noaryl nityl ketone (described later) is 0.8
~2.6 is preferred. If it is less than 0.8, mechanical properties such as strength may not be sufficient, and the molecular weight may decrease during the sulfonation reaction. If it exceeds 2.5, melt moldability is insufficient. Ar, Ar' and Ar in general formula (I)
'' is a divalent aromatic group, and polymers in which these groups are aliphatic or alicyclic groups are not preferred because they have insufficient heat resistance.

The form of the polyaryletherketone to be sulfonated is not limited, and may include powder, granules, molded products, and the like. In the case of powders and granules, the degree of sulfonation can also be controlled by selecting the particle size. In the case of molded products, sulfonation occurs on the surface and vicinity of fibrous, film-like, and various shaped products.

The gaseous or misty compounds used for the sulfonation are conveniently obtained by bubbling an inert gas into the melt or solution of sulfur trioxide, chlorosulfonic acid or fluorosulfonic acid. For example, gases such as air and nitrogen are blown into fuming sulfuric acid, or compounds selected from the group consisting of sulfur trioxide, chlorosulfonic acid, and fluorosulfonic acid are mixed with carbon tetrachloride, carbon tetrabromide, hexachloroethane, etc. A gas such as air or nitrogen may be blown into the solution dissolved in the active solvent. The gas to be blown in preferably does not contain moisture.

The most preferable method of contacting the polyaryletherketone with a gaseous stream (hereinafter referred to as a gaseous stream) containing a gaseous or atomized compound is a method in which the two are brought into contact in countercurrent,
Examples include a fluidized bed type and a sample dropping type. In the case of powdered or granular polyaryletherketones, it is effective to bring them into contact with a gas stream while stirring, and then blow them up or mix them with the gas stream. In the case of fibrous polyaryletherketones, the fibers may be placed or run continuously or intermittently in a gas stream or in an atmosphere in which a gaseous or mist compound is present. Furthermore, in the case of polyaryletherketone in the form of a film, sheet, fiber fabric, etc., only one side can be sulfonated, or the degree of sulfonation can be varied for each side, depending on the application.

Although the sulfonated polyaryletherketone can be used as it is, it is generally used after washing with water and drying. Note that the substituted sulfonic acid group can be converted into a salt, sulfonamide, etc. with an alkali, amine, etc.

(Effects of the Invention) According to the present invention, by bringing the polyaryletherketone into contact with a specific compound in the form of a gas or mist,
The sulfonated polyaryletherketone can be easily separated and recovered from the reaction mixture without causing excessive sulfonation or molecular weight reduction of the polymer that would cause the polyaryletherketone to lose its characteristics. Sulfonated polyaryletherketones can be produced that are easy to control and can be melt-formed with excellent properties.

As shown in the comparative example below, the method of sulfonation with concentrated sulfuric acid has problems such as a decrease in molecular weight, excessive sulfonation, difficulty in separation and recovery, and insufficient properties. This is a simple method.

In contrast, the above-mentioned remarkable effects have been achieved in the embodiments of the present invention.

The sulfonated polyaryletherketone obtained in the present invention can be used alone or as a composition with other polymers or fillers such as glass fiber, carbon fiber, talc, mica, silica, etc. It can be used for various purposes such as membranes, reverse osmosis membranes, biopolymer materials, nuclear reactor materials, and fiber-reinforced composite materials.

(Example) Examples of the present invention will be shown below, but the present invention is not limited thereto. In addition, the physical property values in the examples were determined as follows.

Reduced viscosity: Reduced viscosity of polymer vtS, /C (#/l
) is the polymer concentration 0. Measurements were made at 25°C for a 98% sulfuric acid solution of IP7dl.

Sulfonation rate: The sulfonation rate, which is the degree of sulfonation of the polymer, is the number of -So, H groups per repeating structural unit calculated based on the S/C ratio determined from the elemental analysis value of the sulfonated polymer. It was shown as

Glass transition temperature: The glass transition temperature T7 of the polymer was measured using a differential thermal balance (TG/DTA) Thermo manufactured by Rigaku Denki ■.
Measurement was carried out using a sample volume of 15 to 20 inches using flex' at a heating rate of 10 lF%/min.

Weight loss rate: The weight loss rate of the polymer was determined using a differential thermal balance (TG/DTA) manufactured by Rigaku Denki ■.
sample amount of 15-20 #fI at a heating rate of 10 using
The amount of weight decrease when the temperature was raised from 50°C to 400°C at a rate of °C/min was expressed as a percentage of the original sample amount.

Examples 1 to B, Comparative Example 1 Powder consisting of particles with an average diameter of 260 pm and η8
P/C is 1.86, T is 144℃, and the formula
-+o ()o ()co ()+ Polyaryletherketone (manufactured by IC1, V
ictrex"l'EEK A 60 F) 18
．． Of was placed on top of a G1 glass filter with a diameter of 8a. 6 in a gas generator equipped with a gas inlet and a gas outlet.
Add 200g of oleum and add about 100g of dry nitrogen gas into the oleum at room temperature. The mixed gas consisting of sulfur dioxide and nitrogen gas generated was introduced from the gas outlet to the leg of the glass filter, and was heated with 49 aryl ether ketone at 27°C for 0 minutes (comparative example). 1), 8
minutes (Example 1), 80 minutes (Example 2) and 1 hour (Example 8)
) were brought into contact with each other. The contact-treated polyaryletherketone was thoroughly washed with water and then dried to obtain a sulfonated polyaryletherketone. The products treated according to the present invention (Examples 1-8) contained sulfur element according to elemental analysis compared to the untreated products, the glass transition temperature T1 was increased, and compression molding was possible.

The results are shown in Table 1.

Comparative Examples 2-8 8.02% of the same polyaryletherketone used in Example 1 was dissolved in 98% sulfuric acid 100*/ at 80°C with stirring (it took about 1 hour to completely dissolve). ). Thereafter, at 80°C for further 0 hours (Comparative Example 2) and 8 hours (
Comparative Example 8) Each was stirred. Pour the reaction mixture into water,
The precipitated polymer was separated and collected and then dried.

In the case of Comparative Example 8, the polymer precipitated when the reaction mixture was poured into water contained so much water that it could not be separated and recovered. The results are shown in Table 1.

Comparative Example 4 The same polyaryletherketone used in Example 1 was used at a concentration of 0. For a 98% sulfuric acid solution of IP/dl, 25
Changes in W8P/C over time at ℃ were determined. the result,
Although sulfonation will progress with time (Japanese Patent Application Laid-Open No.
5-86296 and JP-A-57-25828), as shown in Table 2? ,, / Cutting of the polymer main chain from ξ where C is decreased (molecular weight decrease)
is also thought to be occurring.

Table 2 Examples 4 to 5, Comparative Example 6 Powder consisting of particles with an average diameter of 220 PI.
P/C is 1.24. Ty is 156℃ and the formula + 0-
C) A polyaryletherketone having a C0-C repeating structural unit was prepared in the same manner as in Example 1 at 28°C for 0 minutes (Comparative Example 5), 80 minutes (Example 4) and 1 hour (
Example 6) Sulfonation was carried out by contacting each other. The same post-treatment as in Example 1 was carried out to obtain a sulfonated polyaryletherketone. The results are shown in Table 8.

f83 Table Example 6 Sulfonation treatment was carried out at 27° C. for 8 minutes in the same manner as in Example 1 except that chlorosulfonic acid was used instead of 50% oleum. Obtained sulfonated polyaryletherketone paste5. /C was 1.85, T9 was 150°C, and the fluorescent X-ray analysis of the surface of the molded product compression-molded at 400°C was based on S (spectrum was shown).

Claims (1)

[Claims] A repeating structural unit represented by the following general formula (I) -[O-Ar-(O-Ar')-_pCO-Ar'']-
(I) (In the formula, p is 0 or 1, Ar, Ar' and Ar'' are divalent aromatic groups) Polyaryletherketone is combined with gaseous or mist sulfur trioxide, chlorosulfonic acid and fluorosulfonic acid A method for producing a sulfonated polyaryletherketone, the method comprising contacting the sulfonated polyaryletherketone with a compound selected from the group consisting of: