JPS61138627A - Production of aromatic polyketone - Google Patents

Abstract

PURPOSE:To produce the titled polyketone having high polymerization degree in high yield, by reacting a specific compound with phosgene in hydrogen fluoride in the presence of boron trifluoride at a specific temperature. CONSTITUTION:The objective polyketone is produced by reacting an aromatic compound of formula (R<1>-R<12> are H, halogen, hydrocarbon group or alkoxy; X<1> and X<2> are O and/or S; n is 0-5) (preferably diphenyl ether, etc.) with phosgene in hydrogen fluoride in the presence of boron trifluoride at 65-90 deg.C. EFFECT:The objective polyketone having excellent mechanical properties such as tensile strength as well as heat-resistance, dimensional stability, etc. and low hygroscopicity and water-absorption can be produced at an extremely low cost.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing aromatic polyketones.

[Conventional technology]

Aromatic polyketones are known to be polymers with excellent heat resistance, mechanical properties, electrical properties, and dimensional stability, low water absorption, and very good physical properties. In addition, it is known that a polymer with a high degree of polymerization can be obtained by reacting dartenoxypendiyl chloride in hydrogen fluoride in the presence of boron trifluoride as a manufacturing method. However, this method has the disadvantage that an expensive and special reagent called a-phenoxybenzoyl chloride must be used. On the other hand, when polymerization was attempted by reacting diphenyl ether and phosgene, British Patent No. 1. As seen in Example 9 of /6 da, t/7, the yield was very low at 73%.
The glue inh of the product is also 0. l j d&/11, which is very low, and only oligomers are produced.

[Purpose of the invention]

In view of the above points, the present inventors conducted intensive studies and unexpectedly discovered a method for producing aromatic polyketones with a high degree of polymerization at a very low cost by carrying out the reaction at a specific temperature. The gist of the present invention is that in the presence of boron trifluoride in hydrogen fluoride, the general formula (1) ((■) in which R1 to R'1 are hydrogen atoms, halogen atoms,
Indicates a hydrocarbon group or an alkoxy group, xl, X!
represents an acid, an elementary atom or/and a sulfur atom, and n is θ~
The present invention relates to a method for producing an aromatic polyketone, which is characterized by reacting an aromatic compound represented by 5) with phosgene at a temperature of 65 to 0°C.

[Structure of the invention]

To explain the present invention in more detail, the aromatic ethers represented by the general formula (I) used in the present invention include diphenyl ether, bis(j-chlorophenyl)
Ether, bis(,7-methylphenyl)ether, bis(3,!f dimethylphenyl)ether, bis(3-
methoxyphenyl) ether, bis(,y,s dichlorophenyl) ether, bis(3-bromophenyl) ether, bis(3-fluorophenyl) ether, bis(
3,s difluorophenyl) ether, bis(3-ethylphenyl) ether, he≠-diphenoxybenzene,
Bis(enoxifyl)ether, /, y-
Diphenoxybenzene, bis(3-phenoxyphenyl) ether, <t,+'-bis(ti-phenoxy7enyl)diphenyl ether, (ta-phenoxyphenyl)-μ'-phenoxydiphenyl ether, mudabis(3- methylphenoxy)benzene, l, Dervis (
3-chlorophenoxy)benzene, Hehiro-his(3-methoxyphenoxy)benzene, /, Hiro-bis(,7,j
dimethylphenoxy)benzene, mudabis(J-bromophenoxy)benzene, /, kobis(S,S-fluorophenoxy)benzene, diphenyl sulfide,
Bis(3-chlorophenyl) sulfide, bis(3-
methylphenyl) sulfide, bis(3,5-dimethylphenyl) sulfide, (3-methoxyphenyl)
Sulfide, bis(,y,r-dichlorophenyl)sulfide, bis(3-bromophenyl)sulfide, bis(3-fluorophenyl)sulfide, bis(
3,! -difluorophenyl)? le 7 eyed, bis(,
? -ethylphenyl) sulfide, Hegu bis(phenylmercapto)benzene, bis(4'-phenylmercaptophenyl) sulfide, l,3-bis(phenylmercapto)benzene, ≠, Hiro'-bis(Hiro-phenylmercapto phenyl) diphenyl Sulfur ()”, (
4'-phenylmercaptophenyl)-a'-phenylmercaptodiphenyl sulfide, mudabis(3-
methylphenylmercapto)benzene, mudabis(3
-chlorophenylmercapto)benzene, hesene-bis(
3-methoxyphenylmercapto)benzene, /, 3-
Examples include bis(J,5-dimethylphenylmercapto)benzene, Hehiro-bis(3,5-difluorophenylmercapto)benzene, and any of those represented by general formula (I) can be used. It is not limited to. These may be used alone or in combination, and those with 8≠ or/or J structure are preferred. Among these, Karadiphenyl ether, /,
Most preferably, tadiphenoxybenzene, diphenyl sulfide, octap-diphenylmercaptobenzene is used.

In the present invention, the compound represented by the general formula (1) is reacted with phosgene, and the amount of phosgene used is determined by the amount of the compound represented by the general formula (1).
It is usually used in a proportion of at least 7 moles of O, S, preferably at least 7 moles, per mole of the compound represented by 1).

Further, the amount of hydrogen fluoride used in the present invention is determined by the general formula (1)
0.5 to 5θO times the amount (weight ratio) of the compound represented by
Preferably, the amount (weight ratio) of boron trifluoride is - to 100 times that of phosgene.
The molar amount is preferably 0.9 to go times the molar amount.

Is the present invention A5°C or higher? 0℃ or less, preferably 67 to gθ
℃, and when the reaction is carried out at room temperature, only oligomers are produced in low yields, as seen in Example D of the aforementioned British Patent No. 8/4 Hiro, ff/7. do not have. The reason why the reaction progresses when the temperature is raised is that at low temperatures, phosgene and boron trifluoride are difficult to form a complex, so acylation progresses, but when the temperature is raised, phosgene reacts with hydrogen fluoride. It is estimated that chlorofluorocarbonyl or hashifluorocarbonyl is formed, which forms a complex with boron trifluoride, which is likely to react with the compound represented by the general formula CI).

In addition, chlorofluorocarbonyl reacts with a compound represented by the general formula (1) to form an acyl chloride, which reacts with hydrogen fluoride to become an acyl fluoride.
It is presumed that this forms a complex with boron trifluoride and further reacts with the compound represented by the general formula CI) to introduce a ketone bond. In the case of difluorocarbonyl, diacyl fluoride is formed by the above reaction, and it is estimated that a ketone bond is introduced by reacting with boron trifluoride. Also, the temperature is 90℃
Even if it exceeds this level, the degree of polymerization decreases, which is not preferable.

〔Effect of the invention〕

According to the method of the present invention, aromatic polyketones with a high degree of polymerization can be obtained in high yield.

The aromatic polyketones obtained according to the invention have many advantages. In other words, mechanical properties such as tensile strength, bending strength, tensile modulus, and bending modulus, heat resistance, thermal decomposition onset temperature,
Excellent electrical properties and dimensional stability, low moisture absorption and water absorption rate.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Diphenyl ether/, 7θJll (1
0mrno1e) and hydrogen fluoride IO− at 0°C,
Cool to −7 fC and phosgene rcr.

(//g mmols) and hydrogen fluoride 10
-, then add boron trifluoride at 3℃, the pressure will be 1
It became 0Kq/ad. Thereafter, the reaction was carried out at 0°C for at time, and boron trifluoride, phosgene, and hydrochloric acid were purged,
Added to ethanol. The solution is 3N-caustic soda aqueous solution! 00ac, and IN-hydrochloric acid aqueous solution coocr,
It was washed with hot ethanol for 200 hours, washed with water at θθ and oocC in ethanol, and vacuum dried at 720° C. for 1 hour. The yield was 700% (based on diphenyl ether) and the +71 nh measured at 30° C. by dissolving the polymer in 97 sulfuric acid at a concentration of /11/dl was 0.79 dl/1.

Comparative Example: The same reaction as in Example was carried out except that the reaction temperature was 20°C, and the obtained polymer had ηinh = 0. /
It was dVll.

Example C and 3 The reaction temperature (70°C) in Example/ was changed to 6j°C and g.
The reaction was carried out in the same manner as in Example 1 except that the temperature was changed to 0°C. The results are shown in Table/Table 1 Reaction temperature ηinh Example 65℃ 0.20 Example, 7 tO℃ θ, ko Comparative example Example/Except that the reaction temperature in Example/ was changed to 60℃ The reaction was carried out in the same manner as above, but the obtained polymer had a ηinh of 0.04 dl/9.

Sender: Mitsubishi Chemical Industries, Ltd. Attorney for Attorney Hase - 1 other person

Claims (1)

[Claims] (1) In the presence of boron trifluoride in hydrogen fluoride, the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (R^1 to R^1 in the formula (I) ^2 represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and X^1
, X^2 represents an oxygen atom or/and a sulfur atom, and n
is an integer of 0 to 5) and phosgene at a temperature of 65 to 90°C.