JPH0768349B2 - Method for producing aromatic sulfide amide polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an aromatic sulfide amide polymer.

INDUSTRIAL APPLICABILITY The present invention industrially produces a polymer having a chemical structure in which a phenylene group is linked through an amide group and a thioether group and useful as a material for a molded article excellent in heat resistance, solvent resistance, mechanical properties and the like. It is about how to do it.

[Problems to be Solved by Conventional Technology and Invention] Conventionally, as materials for heat-resistant resin moldings, thermosetting,
Various polymers having thermoplasticity are known.

In particular, polyphenylene terephthalamide, polyimide,
Various wholly aromatic heat-resistant polymers such as polyetheretherketone and polyphenylene sulfide are currently being developed in various places.

However, these heat-resistant polymers generally have a problem in molding processability, and also have a problem that the performance is insufficient for applications requiring more severe heat resistance.

Further, many of these heat-resistant polymers have drawbacks such as difficulty in synthesizing the monomer or having to perform polymerization in a special solvent, resulting in poor productivity as a molded product.

An object of the present invention is to provide a method for producing an aromatic sulfide amide polymer having excellent heat resistance, solvent resistance and mechanical properties.

[Means for Solving the Problems] The present invention includes general formulas (I) and (II). ^{X-Ar 4 (R 4)} d -Y (II) ( wherein ^{Ar 1, Ar 2, Ar 3} , Ar 4 represents an aromatic ^{ring, R 1, R 2, R} 3, R 4
Is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and 7 carbon atoms. ~ 20
Represents an aralkyl group and may be the same or different. a, b, c and d are the same or different and each represents an integer of 0 to 4, and X and Y represent halogen, which may be the same or different. ) The amide group-containing dihalide and the aromatic dihalide represented by the formula (4) are sulfided with a sulfidizing agent to produce the aromatic sulfide amide polymer or copolymer.

Examples of the method for synthesizing the aromatic polysulfide amide polymer of the present invention include all methods used for synthesizing polyphenylene sulfide. Particularly, in an organic polar solvent, the amide-based aromatic dihalogen represented by the general formula (I) is used. A method of sulfiding the compound and the aromatic dihalogen compound represented by the general formula (II) with a sulfidizing agent is preferable.

Examples of the amide group-containing aromatic dihalogen compound represented by the general formula (I) used in the present invention include Ar ¹ , Ar ² and Ar ^3. (Z is -O -, - S -, - SO 2 -, - CO -, - CH 2 - or Are shown), etc., and they may be the same or different.

As a preferred specific example thereof, And so on.

These amide group-containing aromatic compounds are preferably composed of a para-position bond from the viewpoint of heat resistance, but in order to improve the solubility and moldability of the resulting aromatic polysulfide amide polymer, the meta-position and / or ortho-position is preferred. May be included.

As a method for synthesizing these amide group-containing aromatic compounds, a general amide bond forming reaction can be used. For example, a method of synthesizing by reacting a corresponding halogen-containing aromatic amine and an aromatic dicarboxylic acid chloride can be mentioned.

The aromatic dihalide (II) used in the present invention includes all the aromatic dihalides described in JP-B-45-3368. Preferred specific examples include dichlorobenzene, dichlorobenzophenone, dichlorodiphenyl sulfone and the like.

The organic polar solvent is preferably an aprotic solvent that is stable to alkali at high temperature. For example, N, N-dimethylacetamide, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, dimethylsulfoxide, N-methyl-
2-pyrrolidone (NMP), 1,3-dimethylimidazolidinone and the like can be mentioned.

The sulfidizing agent used in the present invention may be an alkali metal sulfide, an alkali metal hydrosulfide and an alkali metal base, or a hydrogen sulfide and an alkali metal base. It doesn't matter if it is used in shape.

These sulfidizing agents may be prepared in situ in the system prior to addition of the dihalogen compound represented by the general formula (I) or (II) into the polymerization system or those prepared outside the system. It doesn't matter if added. General formula (I), (II)
It is preferable to remove water in the system by distillation or the like before adding the dihalogen compound represented by the formula to carry out the polymerization so that the amount is 2.5 molar equivalents or less based on the sulfidizing agent. Preferred sulfidizing agents include sodium sulfide, a combination of sodium hydrosulfide and sodium hydroxide, and a combination of hydrogen sulfide and sodium hydroxide.

At the time of polymerization, use of a crown ether compound, which is known as a phase transfer catalyst, a phosphorus salt, an ammonium salt compound, or an auxiliary agent such as an alkali metal carboxylate is effective for improving the molecular weight of the obtained polymer, which is preferable. In some cases.

The polymerization is carried out at 150 to 300 ° C., preferably 180 to 280 ° C. for 0.5 to 24 hours, preferably 1 to 12 hours with stirring.

The ratio of the amide group-containing compound represented by the general formula (I) used in the present invention to the sulfidizing agent is preferably in the range of 0.9 to 1.1: 1, and the amount of the solvent depends on the amount of the polymer produced during the polymerization. It can be used by adjusting to 7 to 50% by weight, preferably 10 to 40%.

The obtained polymer can be isolated by a known recovery method, for example, distillation under reduced pressure, flash method or isolation by reprecipitation with water or an organic solvent, washing with water or an organic solvent, and drying.

The aromatic sulfide amide polymer of the present invention generally has a temperature of 30 ° C.
When dissolved in NMP / LiCl (95/5 weight ratio) to a concentration of 0.1 g / dl, it has an intrinsic viscosity of about 0.02 to 10 dl / g, about 0.05 to
Those having an intrinsic viscosity in the range of 10 dl / g are preferable.

Further, the proportion of constitutional units containing an amide group is small, and in the case of a copolymer which is not completely dissolved in the solvent, when dissolved in chloronaphthalene at 210 ° C. to a concentration of 0.1 g / dl, about 0.02 to 1 is obtained.
It has an intrinsic viscosity of 0 dl / g, preferably in the range of about 0.05 to 10 dl / g.

By heating the aromatic polysulfide amide polymer in the present invention in an oxidizing atmosphere such as in the air, chain extension, crosslinking, branching and the like can be caused.

When molding the polymer of the present invention, various known filler components may be included.

Typical examples of the filler component are: a) fibrous filler; glass fiber, carbon fiber, boron fiber, aramid fiber, alumina fiber b) inorganic filler: mica, talc, clay, graphite, carbon black, silica, asbestos , Molybdenum sulfide, magnesium oxide, calcium oxide and the like.

The aromatic polysulfide amide polymer of the present invention has excellent heat resistance and molding processability, and is useful as a film, fiber and coating material for various molded products.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 0.6 mol of Na ₂ S.2.9H ₂ O; N in a 2 volume autoclave
-Methyl-2-pyrrolidone (NMP) (600 ml) was added, the mixture was stirred under a nitrogen stream, heated to 210 ° C, and dehydrated to obtain 24.2 g of a distillate mainly composed of water. Reaction system at 120 ℃
After cooling down to 0.6 mol was added together with 80 ml of N-methyl-2-pyrrolidone, the system was sealed under a nitrogen stream, the temperature was raised and polymerization was carried out at 240 ° C. for 8 hours. After completion of the reaction, the system was cooled, the contents were put into water, washed with warm water, and the filtration was repeated, then washed with methanol and dried to obtain 179 g of a light gray powdery polymer (yield 86
%) Was obtained.

The intrinsic viscosity of this polymer is 0.25 dl / g (NMP / LiCl; 95/5
The weight ratio was 0.1 g / dl, 30 ° C).

Although melt molding was impossible, it was soluble in concentrated sulfuric acid, NMP / LiCl, etc., and a glossy amber film was obtained by casting from the solution. The infrared absorption of the polymer (IR) from absorbing the thioether bond 1070 cm ^-1 where the spectra were measured, 3260cm ^-1, 1630cm ^-1, the absorption was observed to be derived from an amide group 1500 cm ^-1.

The elemental analysis results showed good agreement with the theoretical values as shown in Table 1.

The decomposition temperature of this sulfide amide polymer was 464 ° C, and no melting point was observed.

Example 2 Polymerization was carried out using the raw materials having the following composition by the same apparatus and method as in Example 1.

The polymer yield was 154 g, and the yield was 90%. The intrinsic viscosity was 0.24 dl / g (NMP / LiCl; 95/5 weight ratio, 0.1 g / dl, 30 ° C). The thermal decomposition temperature was 461 ° C, and a small endothermic peak was observed at 253 ° C. By compression molding this polymer at 320 ° C, a glossy amber film could be obtained.

IR spectrum; 3260,1630,1505cm ^-1 (amide) 1070cm ^-1 (thioether) Example 3 Polymerization was carried out by using the raw material having the following composition in the same manner as in Example 1.

The polymer yield was 145 g, and the yield was 91%. The intrinsic viscosity was 0.21 dl / g (NMP / LiCl; 95/5 weight ratio, 0.1 g / dl, 30 ° C). The thermal decomposition temperature was 488 ° C, and a small endothermic peak was observed at 305 ° C.

IR spectrum; 3270,1630,1505cm ^-1 (amide) 1070cm ^-1 (thioether) Example 4 Polymerization was carried out by using the raw materials having the following compositions and using the same apparatus and method as in Example 1.

The polymer yield was 83 g, and the yield was 93%. The intrinsic viscosity was 0.17 dl / g (chloronaphthalene 0.1 g / dl, 210 ° C). The thermal decomposition temperature is 475 ° C and the melting point is 270 ° C.

IR spectrum; 3260,1630,1505cm ^-1 (amide) 1070cm ^-1 (thioether) Example 5 Polymerization was carried out by using the raw materials having the following compositions and using the same apparatus and method as in Example 1.

After the reaction is complete, N
The MP was distilled off under reduced pressure, the contents were washed with warm water, and filtration was repeated. After washing with methanol and drying, the polymer yield was 150 g, and the yield was 88%.

The intrinsic viscosity is 0.29dl / g (NMP / LiCl; 95/5 weight ratio, 0.1g / d
l, 30 ° C). The thermal decomposition temperature was 457 ° C, and a small endothermic peak was observed at 209 ° C.

IR spectrum; 3260,1630,1505cm ^-1 (amide) 1070cm ^-1 (thioether) The produced polymer was excellent in solubility as compared with the copolymer containing an amide group-containing dihalide having a para bond in Example 2.

[Effects of the Invention] According to the present invention, heat resistance and molding processability are well balanced,
An aromatic polysulfide amide polymer having an amide group can be obtained.

Claims (1)

[Claims] 1. General formulas (I) and (II) ^{X-Ar 4 (R 4)} d -Y (II) ( wherein ^{Ar 1, Ar 2, Ar 3} , Ar 4 represents an aromatic ^{ring, R 1, R 2, R} 3, R 4
Is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and 7 carbon atoms. ~ 20
Represents an aralkyl group and may be the same or different. a, b, c and d are the same or different and each represents an integer of 0 to 4, and X and Y represent halogen, which may be the same or different. ) A repeating unit prepared by sulfiding an amide group-containing dihalide and an aromatic dihalide represented by (Where Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ , R ⁴ , a, b, c, d are the same as above, p / q is 100/0 to 1/99 The method for producing an aromatic sulfide amide polymer or copolymer comprising: