JPH0236233A - Molded article of polysulfone ketone and production thereof - Google Patents

Abstract

PURPOSE:To obtain a molded article of polysulfone ketone having extremely excellent heat-resistance by adding oxygen to a specific molded article of polysulfide ketone. CONSTITUTION:The objective molded article containing the recurring unit of formula II (b is 0-2; l is 0-6) (having an SO2 content of >=50%) is produced by adding oxygen with an oxygen donor to a molded polysulfide ketone composed of the recurring unit of formula I (Ar is bivalent aromatic group such as phenyl, diphenyl, naphthalene, diphenylmethane or diphenylpropane; n is 0-6; m is 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a polysulfocarbon molded product having extremely high heat resistance and a method for producing the same.

(Prior art) In recent years, the development of highly heat-resistant and melt-moldable resins such as polyetherketone and polysulfide ketone has progressed, and due to their good processability, they are used in various applications such as equipment parts exposed to high temperatures, high-performance fibers, and films. Molded products are being developed.

However, although such conventional heat-resistant thermoplastic resins have heat resistance, since they are thermoplastic resins after all, the temperature at which molded products thereof can be used is at most 350°C.

On the other hand, in addition to such resins, there are some known heat-resistant resins such as polyimide and aromatic polyamide whose molded products can be used up to around 400'C. However, such resins are generally difficult to mold and process, and unlike the resins mentioned above, they have the disadvantage of being difficult to form into molded products of various shapes.

(Problems to be Solved by the Invention) An object of the present invention is to provide a molded product with excellent heat resistance and excellent formability, which could not be put to practical use with the conventional techniques, and a method for producing the same. Ru.

(Means for Solving the Problems) In view of the current situation, the present inventors have made extensive studies without being bound by conventional concepts, and have found that the main component is polysulfone ketone (hereinafter referred to as PSOK), which is extremely heat resistant. It was discovered that 1q of molded products with excellent shapeability and shapeability can be produced, leading to the present invention.

The present invention has the following configuration.

(1) In a resin molded product whose main component is a repeating unit represented by the following general formula (I), the repeating unit SO(
However, X is a polysulfone ketone molded product characterized in that the proportion of SO2 in a and b) is at least 50%.

In the above formula (1), Ar is a divalent aromatic group independently selected for each repeating unit from phenyl, diphenyl, naphthalene, diphenylmethane, diphenylpropane, diphenyl ether, diphenyl sulfide, or diphenyl sulfone, and a and b is an integer from O to 2, and α
is an integer from ○ to 6, and m must be 1 or 2.

(2) In the general formula (I>), the repeating unit is SOx
Of which, the proportion of SO2 is at least 70% (1)
The polysulfone ketone molded product described in .

(3) The polysulfone ketone molded article according to (1) or (2), wherein the molded article is one selected from membrane-like materials, granular materials, and fibrous materials.

(4) The polysulfone ketone molded article according to any one of (1) to (3), wherein the fibers constituting the fibrous material are ultrafine fibers of 1 denier or less.

(5) Oxygen is added to a polysulfide ketone molded product whose main component is a repeating unit represented by the following general formula (II) using an oxygen-donating substance to modify it into a repeating unit represented by the general formula (I). A method for producing a polysulfone ketone molded product.

In the above formula (n), Ar is a divalent aromatic group independently selected for each repeating unit from phenyl, diphenyl, naphthalene, diphenylmethane, diphenylpropane, diphenyl ether, diphenyl sulfide, or diphenyl sulfone, and n is O It is an integer of ~6, and m is 1 or 2.

(6) The substance that donates oxygen is an organic peroxide (5
) A method for producing a polysulfone ketone molded product.

The present invention will be explained in more detail below.

The PSOK molded product in the present invention is represented by the following general formula (1) The main component is a repeating unit.

That is, a divalent aromatic group (Ar in the formula) selected from phenyl, diphenyl, naphthalene, diphenylmethane, diphenylpropane, diphenyl ether, diphenyl sulfide, or diphenyl sulfone, and S as defined later.
This is a molded product whose main component is a resin having a structure having a residue represented by Qx and a ketone group. The remaining amount taken here is 1
S at 30° (where X is a and b) is a sulfur atom and O is an oxygen atom. In addition, X is an integer from O to 2 and may be arbitrary for each repeating unit, but when at least 50% of the total is a sulfone group (X = 2), the thermal transition temperature is surprisingly high. This is preferable because the molded product will have revolutionary excellent heat resistance. Furthermore, U can be an integer of 0 to 6, and m can be any number of 1 or 2 for each repeating unit.

In addition, in the present invention, a part of the aromatic ring in the repeating unit may contain a halogen group, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, nitrogen, etc., as necessary, as long as the heat resistance of the molded product is not impaired. It may have a substituent or a bridge structure.

Here, the main component in the present invention means at least 5% of the composition.
It means a component that accounts for 0 mm%, more preferably 60% by weight.

Therefore, as long as PSOK is the main component of the molded product of the present invention, inorganic/organic fiber reinforcing agents such as carbon, fiber, glass fiber, alumina fiber, aramid fiber, liquid crystalline polyester fiber, etc. may be added as necessary. It is used as a molded product containing generally known undefeated fillers such as titanium oxide, talc, graphite, silica, alumina, metal, fluororesin, nylon resin or plasticizer, and other compounding agents. It is possible and necessary.

In addition, the shape of the molded product according to the present invention is a polysulfide ketone (hereinafter referred to as P
SK) may be of any type as long as it can be shaped. For example, injection molded products, sealed products, films, sheets,
Examples include coating films, granules, powders, fibrous materials, etc. Among them, molded products with a large surface area ratio such as film-like materials, granular materials, and fibrous materials are particularly easy to convert from PSK to PSOK. In certain respects, this is a preferred shape in the present invention.

For this reason, membrane-like products such as films and coatings of 10 microns or less, and fibrous products made of fibers of 5 denier or less, more preferably 1 denier or less, are particularly desirable molded products. In particular, when used as a fiber, it is more preferable to have a strength of 0.5C7/d or more and an elongation of 5% or more from the viewpoint of handling properties.

Next, as a method for manufacturing a PSOK molded product in the present invention,
For example, a raw material mainly composed of PSK synthesized by a generally known method using the following raw materials is shaped into a possible shape by a generally known molding method such as injection molding or extrusion molding, and then such PSK molding is performed. This is achieved by bringing a substance into contact with a liquid or gas containing a substance that donates oxygen, thereby adding oxygen to PSK, which is the main component, and modifying it into PSOK.

Here, as a method for producing PSK, for example, at least It can be produced by reacting in an organic polar solvent such as methylpyrrolidone at high temperature and high pressure.

Furthermore, in addition to the ketone component, it is preferable to simultaneously use one or more of the following raw materials, for example.

Next, the substance that donates oxygen in the present invention includes, for example, organic peroxide, unfiltered peroxide, oxygen acid, oxygen, air, ozone, etc. In particular, organic peroxides include It is preferable to use a liquid because the modification reaction can proceed safely and easily.

Here, organic peroxides include performic acid, peracetic acid, perpropionic acid, perbutyric acid, m-chloroperbenzoic acid, pertrichloroacetic acid, perphthalic acid, etc. Among them, the reaction rate is fast, and handling is difficult. The method using peracetic acid is particularly preferred because of its ease of use. In addition, for modification, 1% by weight of 'fJ machine peroxide,
More preferably, a mixed solution containing 3% by weight or more of water, alcohol, or organic acid can also be used, and a catalyst such as a metal can also be added to the colander. Modification of PSK to PSOK by such an organic peroxide is accomplished, for example, by immersing a PSK molded article in a mixed solution containing an organic peroxide, or by applying such a solution and heating it.

The molded products of the present invention can be used, for example, in automobile engine parts that are exposed to high temperatures for long periods of time, electronic and electrical equipment parts, aerospace equipment parts, heat-resistant films, or heat-resistant fibers such as industrial filters, heat-resistant clothing, electrical insulation materials, etc. It can be used for various purposes such as heat resistance w1.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1.2 A polysulfide ketone consisting of a repeating unit of @;r-CD-@-8- synthesized by the method described in Jimon Sho 60-58435 was dried with hot air at 150°C for 15 hours, and then
Spinning was carried out at a spinning temperature of 400'C, a spinning speed of 100 m/min, a 72-hole spinneret, and the following two levels of discharge rate with varying fineness.

Next, both levels were stretched 1.5 times at a stretching temperature of 200°C and heat treated at 250'C.

Table 1 shows the properties of the polysulfide ketone fibers obtained.

Table 1 These fibers were then diluted with 50'C1 of commercially available 9% peracetic acid.
After soaking for 6 hours, it was washed with water and dried.

It was confirmed that all of the obtained fibers were polysulfone ketone fibers with a sulfonation rate of approximately 80% (calculated as 100% when two oxygen atoms were added to all sulfur atoms) (nuclear magnetic resonance spectra). By analysis〉.

Furthermore, the obtained polysulfone ketone fiber had the properties shown in Table 2, and showed a strength retention rate after dry heat treatment at 400° C. for 15 hours, and was surprisingly excellent in heat resistance.

Table 2 Comparative Example 1 The polysulfide ketone fiber obtained in Example 1.2 was treated in the same manner as in Example 1.2 except that it was not treated with peracetic acid, and finally treated at 400'C for 15 hours, resulting in a level 2 Both were unable to maintain their fiber morphology and melted.

Example 3 Polysulfide ketone synthesized in the same manner as in Example 1.2 was dried with hot air at 150°C for 15 hours.
Glass fibers having a length of 3 mm were mixed at a ratio of 380'C1 by weight and press-molded at a pressure of about 10 kCI/Cm2. After molding, the thickness is approximately 1mm, the width is 10mm, and the length is 100m.
The press plate was heat treated at 200°C for 11 hours.

Next, this press plate was immersed in commercially available 9% peracetic acid at 50'C for 12 days, washed with water, and dried.

It was confirmed that the obtained sample was a plate made of polysulfone ketone with a sulfonation rate of 58% (based on nuclear magnetic resonance spectroscopy).

The tensile properties of this plate according to ASTM-D638 were a breaking strength of 4.5 kg/mm2 and a breaking elongation of 0.6%. In addition, the load is 18.6 kg according to ASTM-D648.
The heat distortion temperature of /Cm2 was 470°C.

Comparative Example 2: Load of glass fiber polysulfide ketone molded product obtained in the same manner as in Example 3 except that peracetic acid treatment was not performed.
The heat distortion temperature of 6 kq/cm2 was 310'C.

(Effects of the Invention) The polysulfone ketone molded product of the present invention has epoch-making excellent heat resistance, and according to the manufacturing method of the present invention in which the polysulfide ketone molded product is modified as a raw material, it can be formed into a wide variety of shapes. Molded products with excellent shapeability can be obtained.

Claims (6)

[Claims] (1) A resin molded product whose main component is a repeating unit represented by the following general formula (I), in which SO of the repeating unit is
A polysulfone ketone molded article, characterized in that the proportion of SO_2 in __x (where x is a and b) is at least 50%. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the above formula (I), Ar is independently selected for each repeating unit from phenyl, diphenyl, naphthalene, diphenylmethane, diphenylpropane, diphenyl ether, diphenyl sulfide, or diphenyl sulfone. is a divalent aromatic group, a and b are integers of 0 to 2,
l is an integer from 0 to 6, and m is 1 or 2. (2) In the general formula (I), the repeating unit SO
The polysulfone ketone molded article according to claim 1, wherein the proportion of SO_2 in _x is at least 70%. (3) The polysulfone ketone molded article according to claim (1) or (2), wherein the molded article is one selected from membrane-like materials, granular materials, and fibrous materials. (4) The polysulfone ketone molded article according to any one of claims (1) to (3), wherein the fibers constituting the fibrous material are ultrafine fibers of 1 denier or less. (5) Oxygen is added to a polysulfide ketone molded product whose main component is a repeating unit represented by the following general formula (II) using an oxygen-donating substance to modify it into a repeating unit represented by the general formula (I). A method for producing a polysulfone ketone molded product. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) In the above formula (II), Ar is independently selected for each repeating unit from phenyl, diphenyl, naphthalene, diphenylmethane, diphenylpropane, diphenyl ether, diphenyl sulfide, or diphenyl sulfone. n is an integer of 0 to 6, and m is 1 or 2. (6) The method for producing a polysulfone ketone molded product according to claim (5), wherein the oxygen-donating substance is an organic peroxide.