JPH0141169B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to aromatic polysulfone/polythioethersulfone copolymers, which are novel heat-resistant resins obtained by reacting dihalodiphenylsulfone with diphenols and alkali metal sulfides, and aromatic polysulfone/polythioethersulfone copolymers. The present invention relates to a method for producing a copolymer. [Prior Art] Aromatic polysulfones are well known, for example RN Johnson et al.; J. Polym. Sci., A-152375.
(1967). Such aromatic polysulfones can be obtained as linear aromatic polysulfone polymers by reacting dialkali salts of dihydric phenols with activated aromatic dihalides. Aromatic polysulfone polymers are thermoplastic resins with excellent mechanical properties at high temperatures, as well as good chemical resistance and electrical properties, and are used in electrical and electronic parts, aircraft parts, automobile parts, sanitary food equipment parts, and medical equipment. Practical use is progressing in some parts of machinery and equipment. On the other hand, it is disclosed in JP-A-47-13347 that aromatic polythioether sulfone can be obtained by self-condensation of an alkali metal salt of thiophenol having an activated halogen atom. In addition, it was reported in Japanese Patent Publication No. 53-25880 that dihaloaromatic sulfones can be obtained by reaction with alkali metal sulfides.
In addition, it is described in Japanese Patent Publication No. 53-25879 that aromatic polythioethersulfone with a high molecular weight can be obtained by adding an alkali metal carboxylate, and these polymers have excellent high-temperature properties and moldability. It has also been revealed that [Problems to be solved by the invention] As mentioned above, the aromatic polysulfone polymer has excellent mechanical properties at high temperatures, but the molding fluidity during molding is not necessarily sufficient, and the molding fluidity is poor. It is not suitable for molding precision molded products that require high performance. Therefore, it has not yet been adopted for molding such precision molded products. In particular, improving the mechanical properties and other properties of molded products,
If the amount of filler added is increased for the purpose of reducing costs, the melt viscosity increases accordingly, and once a certain amount is reached, melt blending and melt molding become difficult. There is. On the other hand, although aromatic polythioether sulfone polymers have excellent high-temperature properties and moldability, their mechanical properties, especially impact strength, are not necessarily sufficient, and this is a drawback for molded products. There is a problem that the usage is restricted. In view of the above-mentioned problems, the present inventors have sought to improve the molding fluidity of aromatic polysulfone polymers without impairing their heat resistance and mechanical properties, and to improve the mechanical properties of aromatic polythioethersulfone polymers. Recognizing that it is necessary to improve these materials in order to expand their uses, we have conducted various studies and studies aimed at improving their shortcomings. As a result, in improving the molding fluidity of aromatic polysulfone polymers, it was found that aromatic polythioether polymers have excellent heat resistance and molding fluidity similar to aromatic polysulfone polymers. With this in mind, we have completed a novel aromatic polysulfone/polythioethersulfone copolymer in which both are copolymerized, and a method for producing a high molecular weight copolymer thereof. [Means for solving the problem] The present invention has been made to solve the above problems, that is, the following formula () (However, R ¹ and R ² are the same or different hydrogen, halogen, or a hydrocarbon group having 1 to 8 carbon atoms, and a and b are integers of 0 to 4 and may be the same or different; Ar is indicates a divalent aromatic residue,

【formula】

【formula】

[Formula], where R ³ to R ⁷ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other, and c to e are 0
~4, f, g are integers of 0 to 3 and may be the same or different; Y is a single bond, -O-, -S-, -SO
−，−SO ₂ ，

【formula】

[Formula] R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; m, n
indicates the degree of polymerization and 0<m/m+n<1).
aromatic polysulfone/polythioethersulfone copolymer. Measurement method: 0.5 g/dl concentration in phenol/1,1,2,2-tetrachloroethane = 3/2 (weight ratio),
Measured at 30℃. and expression() (However, X is a halogen and is in the ortho or para position with respect to the sulfone group; R ¹ and R ² are the same or different hydrogen, halogen, or a hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0 〜4 integers which may be the same or different) and the dihalodiphenylsulfone represented by the formula () HO−Ar−OH …() (However, Ar is

【formula】

【formula】

[Formula], where R ³ to R ⁷ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other, and c to e are 0
~4, f and g are integers of 0 to 3 and may be the same or different, Y is a single bond, -O-, -S-, -SO ₂
−、

【formula】 〔Example〕

EXAMPLES The present invention will be specifically explained below using Examples, but it goes without saying that the present invention is not limited to these Examples. Example 1 1.141 g of pisphenol A, 0.835 g of an aqueous sodium hydroxide solution (48.40% by weight), and 5 ml of N-methyl-2-pyrrolidone were weighed into a 100 ml three-necked flask equipped with a stirrer and a cooling tube. After replacing the air in the reaction system with nitrogen, the reaction system was heated to 150° C. with stirring and maintained at that temperature for 10 minutes. The reaction mixture is then cooled to below 100°C, 0.647 g of sodium sulfide (purity 60%) and 20 ml of chlorobenzene are added, and heated again to remove the chlorbenzene present in the reaction mixture as an azeotrope. Water was continuously removed, chlorobenzene was thoroughly distilled off, and the reaction mixture was heated to 150° C. and held for 10 minutes. after that,
The reaction mixture was cooled and 2.872 g of 4,4'-dichlorodiphenylsulfone and 5 ml of N-methyl-2-pyrrolidone were added. After the inside of the reaction system was further purged with nitrogen, it was heated to 150°C and reacted for 14 hours. The obtained reaction product was poured into a large amount of methanol to precipitate a white polymer, and after removing this,
It was washed twice with methanol and twice with hot water, and dried at 100° C. for 5 hours under reduced pressure. The obtained polymer weighed 3.23 g (yield 94%), and the intrinsic viscosity was measured at 30°C at a concentration of 0.5 g/dl using phenol/tetrachloroethane = 3/2 (weight ratio) and found to be 0.20. It was hot. The IR spectrum of this polymer is shown in Figure 1, and the NMR spectrum is shown in Figure 2.
From these figures 1 and 2, the obtained polymer is unit and

〔Effect of the invention〕

The aromatic polysulfone/polythioethersulfone copolymer of the present invention is a novel thermoplastic resin with excellent heat resistance, and the method for producing the same can produce a high molecular weight copolymer with good yield. In particular, the aromatic polysulfone/polythioethersulfone copolymer of the present invention can be molded by ordinary molding methods, but it has a low melt viscosity and therefore has excellent molding fluidity, and can be used with various inorganic or organic materials. It has the characteristic that it can be filled with filler at high density. For this reason, the field of use as a resin composition has been expanded, and it has the special effect of being able to be applied to precision molded parts that require heat resistance, for example, which were previously restricted by fluidity during molding. It is acceptable.

[Brief explanation of drawings]

FIG. 1 shows an IR spectrum chart of the copolymer synthesized in Example 1 of the present invention, and FIG. 2 similarly shows an NMR spectrum chart.

Claims (1)

[Claims] 1 Formula [] (However, R ¹ and R ² are hydrogens that are the same or different from each other,
Halogen, represents a hydrocarbon group having 1 to 8 carbon atoms,
a, b are integers of 0 to 4 and may be the same or different; Ar represents a divalent aromatic residue;
[Formula] [Formula] [Formula], where R ³ to R ⁷ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other, and c to e are 0
~4, f, g are integers of 0 to 3 and may be the same or different; Y is a single bond, -O-, -S-, -SO
-, -SO ₂ -, [Formula] [Formula], R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; m, n
An aromatic polysulfone/polythioethersulfone copolymer having an intrinsic viscosity of 0.1 to 1.5 as measured by the following measuring method, where 0<m/m+n<1 indicates the degree of polymerization. Measurement method: 0.5 g/dl concentration in phenol/1,1,2,2-tetrachloroethane = 3/2 (weight ratio),
Measured at 30℃. 2 formula [] (However, X is a halogen and is in the ortho or para position with respect to the sulfone group; R ¹ and R ² are the same or different hydrogen, halogen, or a hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0 dihalodiphenylsulfone represented by the formula [] HO−Ar−OH …[] (However, Ar is selected from [Formula] [Formula] [Formula] Here, R ³ to R ⁷ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other, and c to e are 0
~4, f, g are integers of 0 to 3 and may be the same or different; Y is a single bond, -O-, -S-, -SO
-, -SO ₂ -, [Formula] [Formula], where R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms) and an alkali metal sulfide are mixed with alkali metal water in a solvent. When reacted in the presence of an oxide or carbonate, the formula [] (However, the symbols in the formula have the same meanings as above.) Intrinsic viscosity 0.1 to 1.5 as measured by the following measurement method
A method for producing an aromatic polysulfone/polythioethersulfone copolymer. Measurement method: 0.5 g/dl concentration in phenol/1,1,2,2-tetrachloroethane = 3/2 (weight ratio),
Measured at 30℃.