JPH04283231A - Aromatic polyether ketone copolymer and its production - 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]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polyetherketone copolymer having a high glass transition temperature, excellent heat resistance, and excellent adhesion to inorganic materials, and a method for producing the same.

0002

[Prior Art] Conventionally, aromatic polyetherketones have been produced by a nucleophilic aromatic substitution type solution polycondensation reaction using two monomers, halogenated benzophenone and hydroquinone (Japanese Patent Publication No. 60-32642, etc.). Polyetheretherketones having two ether groups and one ketone group in one repeating unit are well known.

[0003] Furthermore, by utilizing a nucleophilic aromatic substitution type solution polycondensation reaction of monomers having a site for nucleophilic attack and a site for receiving nucleophilic attack in one molecule, ether groups, There are also examples (such as Japanese Patent Publication No. 47-617) of synthesizing polyetherketones having one ketone group each.

Furthermore, in addition to the above-mentioned nucleophilic aromatic substitution type solution polycondensation reaction, it is also well known to utilize an electrophilic aromatic substitution reaction to synthesize aromatic polyetherketones.

For example, polyetherketoneketone produced by a method using hydrogen fluoride/boron trifluoride (Japanese Patent Publication No. 46
-3392, 47-31440, etc.), polyetherketoneketone produced by a method using a Lewis acid (JP-A-5
9-159826, etc.), polyetherketone by a method using polyphosphoric acid, polyetheretherketone (Kobunshi, 17, 130 (1968)), polyetherketoneketone by a method using trifluoroalkanesulfonic acid (JP-A Publication No. 58-208320, Pol
ymer, 29, 1902 (1988)), polyether ether ketone produced by a method using a mixture of diphosphorus pentoxide and methanesulfonic acid (Japanese Patent Application Laid-open No. 135224/1983), and 4-(4-phenoxyphenoxy ) Polyetheretherketone, polyetherketone (Polyetherketone) synthesized from benzoic acid or 4-(2-methoxyphenoxy)benzoic acid as a self-condensing monomer
Mer Journal, 21, 673 (1989)
), polyether ether ketone produced by a method using trifluoromethanesulfonic acid (JP-A-58-20832
Publication No. 0).

The above-mentioned polyetheretherketone or polyetherketone is mainly a partially crystalline polymer, and its glass transition temperature is about 140°C to 150°C, crystalline melting point is 300°C or higher, and it is a thermoplastic resin. It is extremely high among the

These aromatic polyetherketones take advantage of their excellent heat resistance, toughness, chemical resistance, and radiation resistance, and are used in various fields such as cable wire coating, molded products, films, and fiber filament fields. Application development is progressing.

[0008]

[Problems to be Solved by the Invention] However, these aromatic polyetherketones have poor adhesion to inorganic materials.

[0009] If this drawback can be overcome, it is expected that the use of the polymer as a high-performance, highly heat-resistant polymer will further expand into coating materials for metal materials.

[0010] Although there are examples of introducing functional groups into polyetherketone, the purpose is not to improve adhesion to inorganic materials, and in that case, the temperature at which thermal decomposition starts is 400°C or lower, making it an excellent product. It cannot be said that it has heat resistance (P
Olymer Journal, 21, 673 (1
989)).

The present invention solves the above problems and provides an aromatic polyetherketone copolymer that has a high glass transition temperature, excellent heat resistance, and excellent adhesiveness to inorganic materials. With the goal.

0012

[Means for Solving the Problems] The present inventors have discovered that aromatic polyetherketone has excellent adhesive properties with inorganic materials in addition to its inherent high thermal stability and mechanical strength, making it suitable for use under high-temperature conditions. In order to develop aromatic polyetherketone, the present invention was completed after extensive research.

That is, the aromatic polyetherketone copolymer of the present invention has the general formula

[0014]

[C5]

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms) and 20 to 80 mol% of the structural unit represented by the chemical formula

[0016]

[C6]

An aromatic polyetherketone copolymer comprising 20 to 80 mol% of the structural unit represented by: Furthermore, the method for producing the aromatic polyetherketone copolymer of the present invention can be carried out using the general formula

[0018]

[C7]

4-(alkoxyphenoxy)benzoic acid represented by the formula (wherein R represents an alkyl group having 1 to 4 carbon atoms) and the chemical formula

[0020]

[Chemical formula 8]

The method is characterized in that the above aromatic polyetherketone copolymer is produced by reacting 4-(4-phenoxyphenoxy)benzoic acid represented by the following formula.

General formula of the raw material monomer of the present invention

002
3]

[Chemical formula 9]

4-(Alkoxyphenoxy)benzoic acid represented by the formula (wherein R represents an alkyl group having 1 to 4 carbon atoms) is a known compound, but it is a compound that is a compound of alkoxyphenol and p-halogenated benzonitrile. It can be easily obtained by reacting in the presence of potassium carbonate followed by hydrolysis.

Examples of the 4-(alkoxyphenoxy)benzoic acid include 4-(2-alkoxyphenoxy)benzoic acid, 4-(3-alkoxyphenoxy)benzoic acid, and 4-(2-alkoxyphenoxy)benzoic acid.
(4-alkoxyphenoxy)benzoic acid. Examples of alkoxy include methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 2-methyl-1-propoxy group, 2-methyl-2-propoxy group,
There are 1-butoxy group and 2-butoxy group. These 4-
Any (alkoxyphenoxy)benzoic acid can be used, but in order to obtain a high molecular weight aromatic polyetherketone copolymer, 4-(2 -alkoxyphenoxy)benzoic acid is preferred.

Chemical formula of the other raw material monomer

00
27]

[Chemical formula 10]

4-(4-phenoxyphenoxy)benzoic acid represented by the following is also a known compound, but after reacting 4-phenoxyphenol and p-halogenated benzonitrile in the presence of potassium carbonate, hydrolysis is carried out. You can easily get it if you do it.

The above monomers are preferably used in a purified state by recrystallization in a suitable solvent or the like.

The charging ratio of 4-(alkoxyphenoxy)benzoic acid and 4-(4-phenoxyphenoxy)benzoic acid is 20 to 80% of 4-(alkoxyphenoxy)benzoic acid.
The range of 4-(4-phenoxyphenoxy)benzoic acid from 80 to 20% based on mole % is preferred. If the proportion of 4-(alkoxyphenoxy)benzoic acid is less than 20% by mole, the adhesion with inorganic materials will be poor, and if the proportion of 4-(alkoxyphenoxy)benzoic acid is greater than 80% by mole, the thermal decomposition onset temperature will be 400%. ℃ or less, which is not preferable.

[0031] In order to obtain the aromatic polyetherketone copolymer of the present invention, a known electrophilic aromatic substitution reaction can be used. As a method, for example, a method using hydrogen fluoride/boron trifluoride (Japanese Patent Publication No. 46-3392
, 47-31440, etc.), method using Lewis acid (JP-A-59-159826), method using polyphosphoric acid (Komunshi, 17, 130 (1968)), method using trifluoroalkanesulfonic acid (Unexamined Japanese Patent Publication No. 58
-208320 Publication, Polymer, 29, 190
2 (1988)), a method using a mixture of diphosphorus pentoxide and methanesulfonic acid (JP-A-58-208320, Polymer Journal, 21,673 (1)
989)) and a method using trifluoromethanesulfonic acid (Japanese Unexamined Patent Publication No. 135224/1989).

[0032] Among these, the method preferably used is:
One method uses a mixture of diphosphorus pentoxide and methanesulfonic acid as a condensing agent, and the other uses trifluoromethanesulfonic acid as a condensing agent.

[0033] As trifluoromethanesulfonic acid, a commercially available product can be used as is. As the mixture of diphosphorus pentoxide and methanesulfonic acid, a commercially available product (manufactured by Tokyo Kasei) may be used, or a newly prepared mixture may be used. When preparing, 8 to 8 parts of methanesulfonic acid to 1 part by weight of diphosphorus pentoxide
A mixture of 20 parts by weight can be used, but preferably 9 to 11 parts by weight of methanesulfonic acid per 1 part by weight of diphosphorus pentoxide. Although methanesulfonic acid can be used as a commercially available product, it may be purified by dehydration treatment and distillation under reduced pressure. The amount of condensing agent is not particularly limited as long as it can dissolve the raw materials, but usually 5 to 20 parts of condensing agent per 1 part by weight of raw materials.
Parts by weight range.

In order to produce the aromatic polyetherketone copolymer, the above-mentioned raw materials are dissolved in a condensing agent, and the reaction is continued at a predetermined temperature for a predetermined time. Regarding the reaction temperature, the preferred temperature range varies depending on the raw materials, but it is usually 0 to
The temperature range is up to 140°C. There is no problem in raising or lowering the temperature during the reaction. Reaction time is usually 2~
It is conducted over a period of 100 hours.

After carrying out the reaction for a predetermined period of time, the contents are mixed with water,
Alternatively, the reaction is stopped by dropping it into a basic aqueous solution. If the contents are viscous, they may be diluted with a suitable solvent. The type of basic aqueous solution is not particularly limited, but examples include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, and potassium hydroxide. The produced polymer is finely pulverized and then heated and dried under reduced pressure for several hours to obtain the desired aromatic polyetherketone copolymer.

[0036] The aromatic polyether ketone copolymer obtained here is protected from unstable terminal functional groups by a known method (such as JP-A No. 63-317) to improve its thermal properties. Of course, it is also possible.

[0037]

[Function] The aromatic polyetherketone copolymer of the present invention has high thermal stability due to its constituent repeating units, and excellent adhesion to inorganic materials due to the alkoxy groups of its constituent repeating units.

[0038]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples.

Note that the logarithmic viscosity used as a measure of the molecular weight of the polymer in the present invention is 96
% concentrated sulfuric acid to make 10 ml was used as a sample solution, and the sample solution was measured using an Ostwald viscometer in a constant temperature water bath at 30.0° C. according to the following formula. ηinh=(1n(t/t0))/c where t=sample solution falling time, t0=concentrated sulfuric acid falling time, c=sample concentration (unit: g/dL)

[0040]The glass transition temperature was determined by Seiko Electronics Co., Ltd.
By DSD-200 (under nitrogen, heating rate 10℃/mi
n), thermal decomposition start temperature is Seiko Electronics TG/DTA
-200 (under nitrogen, heating rate 10°C/min),
Infrared absorption spectrum (IR) is manufactured by JASCO Corporation FT-IR
7000 (KBr tablet method), and the nuclear magnetic resonance spectrum (NMR) was measured using JEOL GX-270 (measurement solvent: bisulfuric acid, internal standard reagent: sodium trimethylsilylpropionate-d4).

In order to evaluate the adhesion, a polymer film was prepared on a pickled rolled plate (carbon steel) and evaluated by a grid test (JIS-K5400).

Example 1 4-(2-methoxyphenoxy)benzoic acid 0.0976
g (0.4 mmol) and 0.4896 g (1.6 mmol) of 4-(4-phenoxyphexy)benzoic acid were mixed into a mixture of diphosphorus pentoxide and methanesulfonic acid (weight ratio 1:10).
It was dissolved in 3.6 g and reacted at 80° C. for 24 hours. After diluting with 3 g of methanesulfonic acid at the end of the reaction, it was added dropwise to 200 ml of a saturated aqueous sodium carbonate solution, the resulting polymer was thoroughly ground, heated for 3 hours in 300 ml of a saturated aqueous sodium carbonate solution, and then filtered. Washed thoroughly with water. After washing, it was dried at 120° C. under a reduced pressure of 1 torr for one day. The yield of the obtained polymer was almost 100%, the logarithmic viscosity was 1.02 dL/g, and the glass transition temperature was 156.4°C.
The thermal decomposition initiation temperature was 436.0°C. Moreover, no melting point was observed.

Figure 1 shows the infrared absorption spectrum of this polymer.
The NMR spectrum is shown in FIG. 2, and the elemental analysis values are shown in Table 1.

[0044]

[Table 1]

From the infrared absorption spectrum of FIG. 1, 1228
Absorption based on an ether bond at cm-1 and a carbonyl group at 1655 cm-1 were observed. In addition, the agreement between the analysis results by NMR spectrum and the elemental analysis values was good, and the obtained polymer had the general formula

[0046]

[Chemical formula 11]

20 mol% of the structural unit represented by

[0048]

[Chemical formula 12]

It was confirmed that the desired aromatic polyetherketone copolymer consisting of 80 mol% of the structural unit represented by the following formula was obtained. Further, evaluations regarding the adhesiveness of this polymer are shown in Table 4.

Examples 2 to 3 The same procedure as in Example 1 was carried out except that the ratio of 4-(2-methoxyphenoxy)benzoic acid and 4-(4-phenoxyphenoxy)benzoic acid was changed. The results are shown in Table 4, and the elemental analysis values are shown in Tables 2 and 3. Note that the IR and NMR spectra were almost the same as in Example 1.

[0051]

[Table 2]

[0052]

[Table 3]

Comparative Example 1 In Example 1, 4-(4-phenoxyphenoxy)
The same procedure as in Example 1 was conducted except that 0.4880 g (2.0 mmol) of 4-(2-methoxyphenoxy)benzoic acid alone was used without using benzoic acid. The results are shown in Table 4.

Comparative Example 2 In Example 1, 0.6120 g (2.0 mmol) of 4-(4-phenoxyphenoxy)benzoic acid alone was used instead of using 4-(2-methoxyphenoxy)benzoic acid. The same procedure as in Example 1 was carried out. The results are shown in Table 4.

[0055]

[Table 4]

From the above results, when the proportion of 4-(2-methoxyphenoxy)benzoic acid is increased to more than 80 mol%,
The thermal decomposition onset temperature is 400°C or lower, which means that it cannot be said to have heat resistance (Comparative Example 1), and if the proportion of 4-(2-methoxyphenoxy)benzoic acid is less than 20 mol%, the inorganic material It was found that the adhesiveness was poor (Comparative Example 2).

The polymer of the present invention was also excellent in chemical resistance, radiation resistance, mechanical properties, and electrical properties.

[0058]

Effects of the Invention The aromatic polyetherketone copolymer of the present invention has excellent adhesion to inorganic materials, has a high glass transition temperature, and exhibits excellent thermal stability. Therefore, it can be used for molded products and films used under high-temperature conditions, as well as coating materials for metal materials.

Claims (2)

[Claims] Claim 1: 20 to 80 mol% of a structural unit represented by the general formula, [Chemical formula 1] (wherein R represents an alkyl group having 1 to 4 carbon atoms), and a structural unit represented by the chemical formula [Chemical formula 2] Aromatic polyetherketone copolymer consisting of 20 to 80 mol% of structural units [Claim 2] 4-(alkoxyphenoxy)benzoic acid represented by the general formula, [Chemical formula 3] (wherein R represents an alkyl group having 1 to 4 carbon atoms) and the chemical formula [Chemical formula 4], A method for producing an aromatic polyetherketone copolymer, which comprises reacting the represented 4-(4-phenoxyphenoxy)benzoic acid to produce the aromatic polyetherketone copolymer according to claim 1.