JPH02233729A - Aromatic polyether ketone - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aromatic polyetherketone that is non-destructive and has excellent heat resistance.

[Prior Art] Several aromatic polyetherketones are known to date. For example, an aromatic polyetherketone formed by a desalting polycondensation reaction of hydroquinone and 4,4-difluoropenzophenone was disclosed in Japanese Patent Publication No. 326-1986.
It is publicly known from Publication No. 42. This is already on the market under the trade name Victrex PEEK@.
It is an injection moldable heat-resistant polymer with a glass transition temperature of 144°C and a melting point of 335°C. Also, British Patent No. 1.47
No. 1,171 discloses an aromatic polyetherketone composed of terephthalic acid chloride and 1,4-diphenoxybenzene. Furthermore, JP-A-58-1
An aromatic polyetherketone composed of tetramethylbisphenol A and 4,4'-difluorobenzophenone is also known from JP 01113. It is a non-grade polymer with a glass transition temperature of 235°C.

[Problem to be solved by the invention] Crystalline aromatic polyetherketone has a high glass transition temperature among crystalline melt molding materials, and also has excellent properties in heat resistance, hot water resistance, and alkali resistance. have. However, the aromatic polyetherketone described in the above-mentioned Japanese Patent Publication No. 60-32642 has a melting point of 30
Although it requires a molding temperature close to 400°C because it is over 0'C, the heat distortion temperature of the molded product is approximately 152°C.
°C, which is by no means high compared to other amorphous engineering plastics. Furthermore, although the non-quality aromatic polyetherketone disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 58101113 has somewhat improved heat resistance when compared to crystalline ones, it still cannot be said to have a satisfactory value.

An object of the present invention is to provide a non-grade aromatic polyetherketone having a high glass transition temperature and excellent heat resistance.

[Means for Solving the Problems] The present inventors have continued research on aromatic polyetherketones having various biphenols.

As a result, they found that by using biphenol with a monovalent aliphatic hydrocarbon group as a side chain as a heptanomer, an aromatic polyetherketone that exhibits no crystallinity and has an extremely high glass transition temperature can be obtained. , we have completed the present invention.

That is, the present invention is an aromatic polyetherketone comprising a repeating structural unit represented by the following formula.

(wherein R and R' are each independently selected from monovalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms, and n each represents an integer of 0 to 2.

The aromatic polyetherketone of the present invention is the following compound (A
) and (B) through a polycondensation reaction.

(wherein R and R' are each independently selected from monovalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms, each n represents an integer of 0 to 2, and each X represents a halogen group) ) The compound represented by (A) above includes 3,3'-dimethyl-4,4'-biphenol, 3,3'-di-t-butyl-4,4'-biphenol, 3. 3', 5.5'-tetramethyl-4,4
'-Biphenol, 3,3'dimethyl-5,5'-di-L-butyl-4,4'biphenol, 3.3',
Examples include 5.5'-tetra-t-butyl-4,4'-biphenol, 2.2', 3.3'5.5'-hexamethyl-4,4'-biphenol, and their sodium and potassium salts. can do.

Examples of the compound represented by (B) above include 4.4'-difluoropenzophenone and 4.4'-difluoropenzophenone.

The aromatic polyetherketone according to the present invention is
It is formed by the M4m method described in Japanese Patent No. 7799 and US Pat. No. 3,264,536.

According to a preferred method for producing an aromatic polyetherketone according to the present invention, it is obtained by subjecting the compounds represented by (A) and (B) to a polycondensation reaction in a suitable high-boiling polar solvent. In this case, the non-derivatized starting material monomer may be converted into an alkali metal salt in advance and the post-reaction may be carried out, but preferably the compounds represented by (A) and (B) are added in the presence of an appropriate alkali, and if necessary, the reaction is carried out. It is desirable to add a suitable low-boiling point solvent to remove the moisture present in the polycondensation reaction. Examples of the high-boiling polar solvent used here include dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc., with N-methylpyrrolidone being preferred. Examples of the alkali include sodium metal, potassium metal, sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, etc., and preferably carbonate. Potassium is preferred, in which case the alkali metal is used in excess of at least 5 mol %, preferably 30 to 40 mol %, relative to the hydroxyl groups present. Furthermore, examples of low-boiling solvents that may be used as a water removing agent include toluene and xylene, with toluene being preferred.

The temperature of the polycondensation reaction in the present invention is 150 to 200°C.
is preferable, and more preferably 160 to 190"C. If the temperature is lower than 150°C, the reaction is difficult to occur;
If the temperature exceeds 00°C, side reactions such as decomposition may occur. Although the temperature of the reaction system may be raised to the target temperature all at once, it is preferable to raise the temperature in multiple stages. The time for the polycondensation reaction is 0. 5 to 10 hours is preferred.

In the case of the aromatic polyether sulfone of the present invention, several methods are known for measuring its molecular weight, but the accuracy and reproducibility of the measured values may not be good. In place of the molecular weight of the aromatic polyetherketone thus obtained, the intrinsic viscosity ηrnh (described later) at a constant temperature was used to represent the size of the molecular chain of the solvent-soluble resin in the solvent. The smaller the intrinsic viscosity of the resin, the smaller the molecular size in the solvent, that is, the smaller the molecular weight of the resin. The aromatic polyetherketone of the present invention has an intrinsic viscosity of 0.5 to 5.
df/g, preferably 0.6-3dI! ．． /g.

Intrinsic viscosity is 0. If the molecular weight is less than 5 d f /g, the molecular weight is low, the heat resistance is poor, and the physical properties of the molded product may be insufficient. Moreover, many of those having an intrinsic viscosity exceeding 5 dl/g are difficult to mold.

The aromatic polyetherketone according to the present invention can be used as a film,
It can be molded into various shapes and used.
It has excellent properties such as high heat resistance, low coefficient of linear expansion, mechanical properties, and electrical properties.

[Example] Examples of the present invention will be shown below, but the present invention is not limited thereto. In addition, the method of measuring physical properties in Examples is as follows.

Intrinsic viscosity: sample resin 0. Dissolve 5 g in 20 mffi of N-methylpyrrolidone, and 10 mj2 of it
was placed in an Ostwald viscometer and immersed in a constant temperature bath adjusted to 30±0.5°C, and after the temperature reached a sufficient constant temperature, the falling time t between the viscometer gauge lines was measured. Falling time L of only the solvent measured in advance. and the solution concentration C, the characteristic coefficient η is calculated by the following formula:
．． , was sought.

77 inh = In(t/to) /c Infrared absorption spectrum Fourier transform infrared spectrometer FT manufactured by Nippon Bunko ■
/■ Using R-5000, measurements were made on a film prepared by a solvent casting method.

Glass transition temperature: Differential scanning calorimeter DS manufactured by Shimadzu Corporation
Using C-41, a sample resin film 5IIIg created by the solvent casting method was heated in nitrogen at a temperature increase rate of 10'C/min. The temperature at which the calorific value began to change was determined as the glass transition temperature from the thermogram. .

Weight loss: Using a thermobalance TGA-40 manufactured by Shimadzu Corporation, measure the change in weight over time when a sample resin film 5 created by the solvent casting method was heated in air at a heating rate of 10°C/min. did. Also, from this measurement value,
The temperature at which the weight loss rate was 10% relative to the original weight was determined.

Actual penetration ↓ 0.01 mol of 3.3', 5.5' -Te1-
lamethyl 4.4'-biphenol, 0.01 mol of 4
, 4'-difluoropenzophenone, 0.014 mol potassium carbonate, 0.21 mol N-methylpyrrolidone, and 0. 1. Add 4 moles of toluene to the mixer.
The reactor was charged to a reactor equipped with a nitrogen supply conduit, a Dean-strak trap, and a cooling tube and heated to 150° C. in a nitrogen atmosphere. The temperature was then slowly raised to 160°C over a period of 6 hours while toluene was distilled off, and the reaction was then carried out at this temperature for 3 hours to obtain a highly viscous and viscous reaction solution. The reaction solution was filtered while hot to remove inorganic salts, neutralized with acetic acid, and poured into methanol:water=1:1 to coagulate the polymer. The polymer was filtered, washed with water and methanol, and dried overnight at 80"C under reduced pressure to obtain the desired polymer. The intrinsic viscosity of this polymer was 1.22 di/g, chloroform, and tetrahydride. It was possible to obtain a transparent and tough film that was soluble in furan, 1,4-dioxane, and the like.

The infrared absorption spectrum of this polymer film is shown in Figure 1.
The elemental analysis values are shown in Table 1 below.

(Table 1) C (χ) H (χ) Calculated value 82.83 5.75 Measured value 8
1.96 5.61 From Figure 1, the absorption of C=0 stretching vibration at 1656cl' is l229, 1015cm-
Absorption of antisymmetric and symmetric stretching vibrations of C-O-C was observed in ', respectively, and the agreement of the elemental analysis values was also good, confirming that the desired polymer was obtained. The glass transition temperature of this polymer was 153°C, and no melting point was observed. This weight body showed no decrease in weight up to 420''C, and the temperature at which it showed a weight loss rate of 10% with respect to the original weight was 505°C.

Disaster relief I 0.01 mole 2.2', 3.3', 5.
5'-hexamethyl-4,4'-biphenol, 0
．． Ol mol of 4,4'-difluorobenzophenone, 0
．． 0.14 moles of potassium carbonate, 0.21 moles of N-methylpyrrolidone, and 0.14 moles of toluene were added to the reaction as in Example 1.

Intrinsic viscosity of the obtained polymer ηr-h = 1. 5 5
dj! /g1 chloroform, tetrahydrofuran, 1.
A transparent and tough film was obtained which was soluble in 4-dioxane and the like. It was confirmed from the infrared absorption spectrum (Figure 2) and elemental analysis values (Table 2) of the polymer film that the desired polymer was obtained.

(Table 2) C(χ) H(χ) Calculated value 83.01 6.29 Measured value 8
2.26 6.07 This polymer showed a glass transition temperature of 268°C and no melting point was observed. The polymer is 38
No weight loss up to 0°C, lO% of original weight
The temperature at which the weight loss rate was shown was 460°C.

[Brief explanation of the drawing]

1 and 2 are diagrams showing the IR spectra of the polymer films obtained in Examples 1 and 2.

Claims (1)

[Claims] An aromatic polyetherketone consisting of a repeating structural unit represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R and R' are each independently selected from monovalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms, and n is each an integer of 0 to 2. )