JPH01226867A - Production of phenylenethioether oligomer - Google Patents

Abstract

PURPOSE:To provide the subject oligomer by reacting dibromobenzene with 4-halo thiophenol alkali metal salt in an aprotic polar solvent, or to provide a functional group-terminated oligomer by further reacting the product with an aromatic mercaptide. CONSTITUTION:An oligomer of formula I (X<1> and X<2> are halogen; m is 1-10) is obtained by reacting dibromobenzene with 4-halo thiophenol alkali metal salt in an aprotic polar solvent (e.g., DMF) at 170-230 deg.C for 5-15hr. The obtained oligomer is reacted with a compound of formula II (Y is NH2, OH, CH, etc.; M<1> is Li, Na or K) at 160-230 deg.C for 3-12hr to provide an oligomer of formula III. The oligomer is useful as a raw material for crystalline aromatic- poly(thio)ether, -polyamide, -polyimide, -polyester, etc., and also as a moldability- improving agent for heat-resistant resins. The above-mentioned method provides the objective compound in a high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing phenylenethioether oligomers. The phenylene thioether oligomer produced by the present invention is a crystalline heat-resistant resin (crystalline aromatic poly(
thio)ether, crystalline aromatic polyamide, crystalline aromatic polyimide, crystalline aromatic polyester, etc.),
It is useful as a moldability improving material for heat-resistant resins.

[Conventional technology]

It is known that a polyphenylene thioether polymer can be obtained by reacting an aromatic di-rogen compound with an alkali gold sulfide (for example, as disclosed in Japanese Patent Publication No. 45-336).
No. 8, Japanese Patent Publication No. 52-12240, etc.), and is widely used in practical use as a typical super engineering plastic.

On the other hand, the low-molecular weight polymer has a high crystalline 1·t/chemical resistance even when it is a trimer to tetramer, and also has a heat resistance/flow of 41]'i
Because of its excellent lability, it is useful as a raw material for crystalline heat-resistant resins, a moldability improving material for heat-resistant resins, and the like. When used for such purposes, the presence of a polymer having 1011Ii or more (polyphenylene thioether) is undesirable; in other words, the performance of the resin produced using it as a raw material may deteriorate, or the moldability improving material may deteriorate. When used as an oligomer, the dispersion state deteriorates, so it is necessary to control the production of oligomers of 10 or less.

[Problem to be solved by the invention]

There are several methods that have been proposed to date as a method for producing such low molecular weight phenylenethioether oligomers (Polymer Bulletin, etc.).
n), Vol. 4, p. 459 (1981), Viakromol Chem (+viakromolChem)
), Vol. 184, p. 779 (1983), JP-A No. 61-7248, etc.) use alkali metal sulfides as the S source, resulting in radical polymerization and formation of low-molecular weight polymers. It was impossible to obtain only the oligomers in high yield.

[Means to solve the problem]

As a result of intensive research into a method for obtaining only low-molecular-weight phenylenethioether oligomers, the present inventors found that by reacting dibromobenzene and 4-halothiophenol, an organic solvent free from high-molecular-weight substances with a melting point of 2,000 or higher was found. The present inventors have discovered that soluble phenylenethioether oligomers can be obtained in high yield, and have completed the present invention.

That is, the present invention provides phenylenethio
The present invention provides a method for producing a fluorolycomer.

(11 cyphyromobenzene (1) 4-halothiopheno-& fluorine metal salt (It) is reacted in an aprotic polar solvent to form the formula (III) (where x, x''
, x'' represents a halogen atom, and M represents an alkali metal.

Moreover, m is an integer of 1 to 10. ) A method for producing an organic solvent-soluble phenylenethioether oligomer.

and (2) the resulting organic solvent soluble phenylene thioether oligomer of formula (IV) (wherein Y is NH
z, OH, C02R, or CN. M
l is either Li, Na, or Ni. ) A method for producing a terminally functional phenylenethioether oligomer represented by formula (v) by reacting an aromatic mercaptide represented by the following in an aprotic polar solvent.

Dibromobenzene (I) used in the present invention
-Dibromobenzene, m-dibromobenzene, p-dibromobenzene, and four compounds thereof can be mentioned, but from the viewpoint of reactivity/product performance, p-dibromobenzene should be used in an amount of 80% or more, preferably 90%. Those containing the above are used.

7 A of 4-7·of thioenol used in the present invention
fy IJ Gold J4j [(II) Obtained by reaction of u,4-halo-1-ofenol with a basic alkali metal compound. 4-halothiophenol d is a compound represented by the following formula (Vl). In addition, basic alkali metal compounds include (1) 7" metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.) (ii) fulkali metal carbonates (lithium carbonate, sodium carbonate, etc.) potassium carbonate, etc.) (iii) Alkali metal alkoxides (sodium methoxide, potassium t-butoxide, etc.) (iv) Alkali metal hydrides (sodium hydride, potassium hydride, etc.) (V) Alkali metal alkylates (methyllithium, n
-butyllithium, etc.), but particularly preferred are (1) alkali metal hydroxides and li) alkali metal carbonates.

The method for preparing the alkali metal salt (■) of 4-halothiophenol is to add 1.05 to 1.2 equivalents of a basic alkali metal compound to 1 mole of 4-halothiophenol (N) in an aprotic state. Obtained by reaction in a polar solvent.

At this time, it is preferable to add larakishime and dibromobenzene, since this suppresses the formation of phenylenethioether polymer due to self-condensation of the formed salt (It).

In the present invention, dibromobenzene (1) 4-...
The molar ratio of lothiophenol to alkali gold fii (■) is in the range of (II) / (1) = 1-4. If it is less than 1, fl of dibromobenzene (1) will be present, while if it is more than 4, organic solvent insoluble matter will be produced, which is not preferable.

The oligomer production reaction of the present invention is carried out in an aprotic polar solvent.

Specific examples of non-10 ton polar solvents used in the present invention include linear amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethelbenzabad, and N-methyl Pyrrolidone, N-methyl-
1-Cyclic iodo interpolants such as caglolactam, N, N, N'
, N'-tetramethylurea, substituted urea solvents such as 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane, hexamethylphosphonamide, and the like. At least one of these is used. Among them, N,N-dimethylacetamide, N-methylpyrrolidone, N,N,N',N'-tetramethylurea,
1,3-dimethyl-2-imidazolidinone and the like are preferred.

In the present invention, the reaction temperature is maintained in the range of 150-250°C, preferably 170-230°C.

If the temperature is higher than 250°C, high molecular weight substances are likely to be formed, and father,
If the temperature is lower than 150°C, the yield will decrease, which is not preferable.

In the present invention, the reaction time ranges from 2 to 20 hours, preferably from 5 to 15 hours. If the time is longer than 20 hours, high molecular weight substances are likely to be produced, and if the time is shorter than 2 hours, the yield will decrease, which is not preferable.

In the present invention, it may be preferable to add a small amount of a radical scavenger (-seijin transfer terminator) typified by m-dinitrobenzene and p-dinitrobenzene, or a chain transfer terminator typified by t-dodecylmercaptan. however,
Many of these react with the products in this reaction system, so
It is necessary to suppress the amount used to 1 mol% or less based on dibromobenzene (1). Among these, m-dinitrobenzene is preferred (because it hardly reacts with the product).

By reacting under the above conditions, organic solvent soluble (
In other words, it is possible to obtain a phenylenethioether oligomer (which does not contain a high molecular weight substance).

The performance of the resin produced using this as a raw material and the dispersion width when used as a moldability improving material are good.

The ends of this oligomer are essentially halogen atoms,
It can be used by itself as a raw material for crystalline heat-resistant resins such as crystalline aromatic poly(thio)ether, or as a moldability improver for heat-resistant resins, but it can also be used as a material for improving the moldability of heat-resistant resins. , OH.

It is preferable to have C0zH, CN) at the end.

In order to obtain a phenylene thioether oligomer having a halogen terminal and a y-terminus, 1.2 to 3 moles expressed by the following formula (IV) per halogen terminal are added to the phenylene thioether oligomer (... halogen terminal) obtained by the above method. What is necessary is to react the aromatic mercaptide in an aprotic polar solvent.

(In the formula, Y represents any one of NHZ, OH, CO2R, CN. Ml is any one of Li, Na, and K.) Such an aromatic mercaptide is an aromatic mercaptide represented by the formula (■) Obtained by the reaction of group mercaptans with alkali metal bases. Specific examples of aromatic mercaptans include m-
aminothiophenol, p-aminothiophenol, m
-Mercaptophenol, p-mercaptophenol,
Examples include methyl p-mercaptobenzoate and p-cyanothiophenol. On the other hand, examples of the alkali metal base include sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.

Generally, for 1 mole of the above aromatic mercaptan,
1.05 to 1.2 equivalents of an alkali metal base are reacted in an aprotic polar solvent to obtain an aromatic mercaptide of formula (Fly).

The aprotic polar solvent used in this case is:
Solvents used in the method for producing the phenylene thioether oligomer can be used.

In the present invention, the aromatic mercaptate represented by the formula (r/) is 1.2 to 3 equivalents (preferably 1.5 to 2.5 equivalents ft) per halogen terminal of the phenylene thioether.
) using phenylenethioether oligomer and 150
1-20 at ~250°C (preferably 160-230°C)
By reacting for a period of time (preferably 3 to 12 hours) in an aprotic polar solvent, a terminal I-II phenylenethioether oligomer is obtained. Compared to the raw material, this oligomer has a higher molecular weight and a higher melting point due to the terminal modification, but it is soluble in organic solvents (sometimes aprotic polar solvents).

This oligomer is a crystalline aromatic poly(thio)ether, a crystalline aromatic polyamide, a crystalline aromatic polyimide,
In addition to being useful as a raw material for crystalline heat-resistant resins such as crystalline aromatic polyester, it can also be used as a moldability improver for heat-resistant resins because the fractional state is controlled by interaction with the resin due to the presence of terminal functional groups. is also more effective.

The phenylene thioether oligomer (...rogen-terminated or terminal-functionalized) of the present invention is easily isolated by pouring the reaction mixture into water and washing the precipitate with water and then with methanol.

〔Example〕

EXAMPLES Below, in order to further clarify the effects of the present invention, Examples will be specifically described, but the scope of the present invention is not limited to these Examples.

Example 1 A 1t8 four-north flask equipped with a nitrogen gas inlet, a thermometer, and a water separator with a Dimroth condenser was charged with 23.6 ml of p-cyphyromobenzene. (0.10 moA-) and potassium carbonate 22.1 ? (0.16 mol) and 100aj of N-methinepyrrolidone (NMP) were charged, and the temperature was raised to 150°C over 1 hour under a nitrogen atmosphere.

Next, a solution containing 43.49 (0.3 mol) of p-chlorothiophenol dissolved in NMPl 00dK was heated to an internal temperature of 15 dK.
The mixture was added over 3 hours while being maintained at 0 to 160°C, and then maintained at 170 to 175°C for 10 hours. After cooling to room temperature, the reaction mixture was poured into water, and the resulting solids were washed individually with water to remove inorganic salts. Thereafter, it was washed with methanol to remove raw materials and the like, and vacuum dried at 50 to 80°C for 8 hours to obtain a light pink powder.

From the IR spectrum, thioether absorption is seen at 1085 cm, while 2400-2700 c! No absorption was observed in the R region (mercaptan absorption region), and the terminal was essentially rogen.

It was soluble in mata, hot toluene, N-methylpyrrolidone, etc., and no high molecular weight product was produced. This was confirmed by differential thermal analysis (Du Pon
t 910 I) differentiaffi Sca
nningCalorimeter)
This was also supported by the fact that there was no polymer having an endothermic peak derived from the melting point at 00-175°C (centered at 140°C) and an endothermic peak at 200°C or higher.

Examples 2 to 3, Comparative Examples 1 to 4 The same method as in Example 1 was carried out using a pond in which the type of solvent, the type of dihalogen, and the ratio of p-chlorothiophenol to dihalogen were as shown in Table 1. .

The results are shown in Table-1.

Table 1 shows that when a compound other than dibromobenzene is used as a dihalogen, a high molecular weight substance insoluble in organic solvents is produced (Comparative Examples 1 to 3), or a bar SH-terminated phenylenethioether oligomer is produced (Comparative Example 4), so it is clear that this is not desirable.

(Left below) Example 4 A 1000 d capacity four-sided flask equipped with a nitrogen gas inlet, a thermometer, and a water separator with a Dimroth condenser 17.
p-dihalogen > 23.6 f (0.10 mol)
and potassium carbonate22. I P (0.16 mol) and 1
．． 3-dimethyl-2-imidazolidinone (DMI) lo
om was charged, and the temperature was raised to 150° C. over 1 hour under a nitrogen atmosphere.

Next, p-chlorothiophenol 43.4 f (0,3
A solution of 0 mol) dissolved in DMllood was heated to an internal temperature of 1
The mixture was added over 3 hours while being maintained at 50 to 160°C, and then maintained at 170°C for 10 hours. Cool to 120℃,
Next, 27.6 t (0.20 mol) of potassium carbonate was added, and further p-aminothiopheno-^45.0? (
A solution of 0.36 mol) dissolved in DMllood was added over 0.5 hours while maintaining the internal temperature at 150 to 160°C. Thereafter, the temperature was maintained at 165-175°C for 12 hours.

After cooling to room temperature, the reaction mixture was poured into water, and the resulting solids were washed individually with water to remove inorganic salts. Subsequently, it was washed with Meta/-A to remove raw materials, etc., and dried at 50 to 60°C for 8 hours to obtain a pale cream-colored powder with an IR spectrum of 50.9 f, around 3300 an, and 160
Absorption derived from amines was observed near 0cPR and 1270cm, and thioether absorption was observed at 11090c.On the other hand, almost no rogen atoms were detected, and the terminal was substantially amine.

Further, it was soluble in hot acetone, N-methylpyrrolidone, etc., and no high molecular weight substance was produced. This was confirmed by differential thermal analysis in nitrogen water at a heating rate of 10°C/min.
This was supported by the fact that there was no polymer having an endothermic peak derived from the melting point at ~115°C (centered at 90°C) and an endothermic peak at 200°C or higher.

Q Application evaluation example 100 parts of dioete h-based resin (η
inh = 0.80dll? (0.2%N M P
solution, 30°C). Tg=227°C], (m/n=go/2o), phenylenethioether oligomer (obtained in Example 3 or Comparative Example 2), and 500 parts of NMP were mixed and stirred at 100°C. As a result, when the oligomer of Example 3 was used, a completely homogeneous solution was obtained, and no precipitate was formed even after cooling to room temperature, but when the oligomer of Comparative Example 2 was used, a completely homogeneous solution was obtained. A uniform solution was not obtained, and it was difficult to uniformly disperse the oligomer in the resin.

Patent applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Masahisa Nagatani Agent Patent Attorney Takaya Yamamoto

Claims (2)

[Claims] (1) Dibromobenzene (I) and an alkali metal salt of 4-halothiophenol (II) are reacted in an aprotic polar solvent to form the following formula (III) ▲Mathematical formula, chemical formula, table, etc.▼ (III) (In the formula, X^1 and X^2 represent halogen atoms. Also, m is an integer of 1 to 10.) A method for producing a phenylenethioether oligomer. (2) An organic solvent-soluble phenylenethioether oligomer obtained by reacting dibromobenzene with an alkali metal salt of 4-halothiophenol and the following formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) (In the formula, Y represents either NH_2, OH, CO_2R, or CN. M^1 is Li, Na, or K.) The aromatic mercaptide represented by is reacted in an aprotic polar solvent. Then, the following formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, Y represents the same meaning as in formula (IV), and m is 2 to 1.
Indicates an integer of 0. ) A method for producing a terminally functional phenylenethioether oligomer.