JPS61247736A - Production of branched phenylene sulfide polymer - Google Patents

Abstract

PURPOSE:To produce the titled inexpensive polymer which is improved in melt viscosity and requires no step of heat curing, by reacting specified two compounds with an alkali metal sulfide in an organic polar solvent. CONSTITUTION:A mixture (A) is obtained by mixing a terphenylene polyhalide of the formula (wherein X, X' and X'' are each F, Cl, Br or I, 1, m and n are each 0 or 1-3 and 1+m+n=4 or 5) at a molar ratio of 0.001-0.02:1. A mixture (C) is obtained by mixing 8-1.2 mol, per mol of component A, of an alkali metal sulfide (B) (e.g., Na2S) with 20-30 mol, per mol of component B, of an organic polar solvent (e.g., N-methyl-2-pyrrolidone). Components A and B are mixed with each other and polymerized at 150-300 deg.C for 0.5-10 hr in an inert gas atmosphere. After the reaction, the reaction mixture is cooled, filtered, washed with water and dried to obtain a branched phenylene sulfide polymer.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a method for producing a high melt viscosity without thermal curing.
The present invention relates to a method for producing a branched phenylene sulfide polymer.

The branched phenylene sulfide polymer of the present invention with improved melt viscosity can be used as films, sheets, fibers, coating materials, extruded products, and the like.

<Prior art> Polyphenylene sulfide (hereinafter abbreviated as rPP8J) shown below has been known as one of the aromatic sulfide polymers, and PP8 is a thermoplastic resin with high heat resistance. Useful as parts and electrical components.

As a general method for producing PPS, a method is known in which, for example, p-dichlorobenzene and sodium sulfide are reacted in an organic amide solvent such as N-methylpyrrolidone (Japanese Patent Publication No. 3568/1983).

Although this method is excellent as an industrial production method, the obtained PPS has a low melt viscosity and is difficult to use without a heat curing step. Further, even after thermosetting, the brittleness is not sufficiently improved, so it is not suitable for thick molding or film formation.

As an improved polymerization method for obtaining PPS with high melt viscosity, a method has also been proposed in which an alkali metal carboxylate is added as a polymerization aid to the above reaction system (Japanese Patent Publication No. 52
-12240). However, this method uses large amounts of expensive alkali metal salts of organic carboxylic acids;
There are problems such as increased production cost and difficulty in post-treatment of the polymerization reaction product.

As a branched sulfurized arylene polymer Omu method, N
- in methylpyrrolidone solvent, for example Paraziq eICI
A method of contacting benzene with an alkali metal sulfide, lithium carboxylate or lithium chloride, 1,2.4- A reaction mixture consisting of paradihalobenzene, an alkali metal sulfide, an alkali metal hydroxide, and an alkali metal carboxylate is polymerized in an organic ide solvent, and at the end of the polymerization, for example, 1,2,4-trichlorobenzene is added for reaction. A method for doing so has been proposed (Japanese Patent Laid-Open No. 56-28217).

However, both methods have high cost and
There are problems such as post-treatment of reactants or wastewater treatment becoming difficult.

<Problems to be Solved by the Invention> The present invention provides a branched phenylene sulfide polymer with improved melt viscosity, and furthermore, it is possible to perform a heat curing process without using expensive polymerization aids. This was done with the aim of providing a method for producing unnecessary phenylene sulfide polymers at low cost.

Means for Solving Problems> As a result of intensive research to achieve the above object, the present inventors have developed a general formula [wherein X, XI, Xll are F, CL,
Br or IJl [indicates a child and may be the same or different from each other. t, m, n represent 0 or an integer from 1 to 3, and L −)−m 10n = 4 or 5]
A terphenylene polyhalide and a polyhalogenated benzene represented by the above are combined in a molar ratio of terphenylene polyhalide/polyhalogenated benzene of 11001 to 0.
．． It has been found that a branched phenylene sulfide polymer with a high melt viscosity can be obtained by coexisting with alkali metal sulfide in an organic polar solvent in a range of 0.02.

The branched phenylene sulfide polymer of the present invention contains terphenylene polyhalide in a molar ratio of Q, O°01 to α02, preferably α
It can be obtained by convenient use in the range of 005 to α01.

If the amount of terphenylene polyhalide is less than (L O0,1), the desired improvement in melt viscosity is not sufficient, while if it is more than α02, melt fluidity tends to be lost.

The method of the present invention will be explained in more detail.

Terphenylene polyhalides used in summer in the method of the present invention include 2,4.4',4''-tetrabromo-m-terphenyl, 4.2/, at, all-tetrabromo-m-terphenyl, a , 31. al.
, all-tetrabromo-〇-terphenyl, 2,
4, 21: all-tetrabromo-p-terphenyl, 2,416.2'f4''-pentabromo-p-terphenyl, etc., and these can be used alone or as a mixture for summer use.

Examples of polyhalogenated benzene include p-dichlorobenzene, p-')bromobenzene, m-dichlorobenzene,
Examples include 0-dichlorobenzene and trichlorobenzene. Among these, dichlorobenzene can be used alone or in combination for summer use.

Examples of the alkali metal sulfide include sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, and two or more of these may be used in combination, and either anhydrous or hydrated forms thereof may be used.

Alternatively, these sulfides may be alkali metal sulfides produced by directly adding an alkali metal bisulfide and an alkali metal hydroxide to the polymerization reaction system and allowing the two to react within the polymerization reaction system.

As the organic polar solvent, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, N,N-dimethylformamide, acetamide, N-methylformamide, N,
Examples include N-dimethylacetamide, 1,3-dimethyl-2-idazolidine, 1-cagrolactam, hexamethylphosphoramide, tetramethylurea, sulfolane, dimethylsulfolane, and N-methyl-2-pyrrolidone is preferred. .

In the method of the present invention, the amount of alkali metal sulfide is usually 118 to 1.2 in molar ratio to the total amount of polyhalogenated benzene and terphenylene polyhalide;
Preferably it is 0.9 to 1.1.

The amount of the organic polar solvent in the case is usually 2.0 to 20 times, preferably 3 to 10 times, in molar ratio to the alkali metal sulfide.

When carrying out the method of the present invention, first, an alkali metal sulfide is added to an organic polar solvent, the temperature is raised while stirring in an inert gas atmosphere, and most of the water in the system is leached out under normal pressure. Perform operations. The temperature for wetting water is 100~2
00°C, preferably 145-200°C. The amount of water leached out depends on the amount of hydration water of the alkali metal sulfide, but the amount of water remaining in the alkali metal sulfide
It is preferable that the amount is 1.3 mol or less.

If more water remains than this, it is not preferable because the yield of the polymer decreases or variations in quality are observed. There are no particular restrictions on the rate of water wetting out, but in order to prevent rapid wetting of water or to ensure good separation of water and solvent, the temperature may be raised slowly if a condenser is attached.
It is preferable to let the water drip out gradually.

After the above dehydration operation is completed, the system is cooled to 150 to 170°C, and polyhalogenated benzene and terphenylene polyhalide are added thereto.

Both can be added separately or in a mixture, or dissolved in the organic polar solvent used for the bait.

Next, the reaction system was sealed under an inert gas atmosphere or slightly pressurized with an inert gas, and the temperature was raised with stirring to 150-3
The polymerization reaction is carried out at 00°C, preferably 200-280°C, for 5-10 hours. After the reaction is completed, the contents are taken out after cooling, and the branched phenylene sulfide polymer of the present invention is obtained by repeating filtration, washing with water, washing with a solvent (acetone or methanol, etc.), and drying.

Furthermore, if necessary, the heat resistance and mechanical strength of the branched phenylene sulfide polymer can be further improved by heat curing at 100 to 280°C in the presence or absence of oxygen. .

The branched phenylene sulfide polymer according to the present invention 1c includes:
As reinforcing fillers, inorganic fibers such as glass fiber, asbestos fiber, carbon fiber, alkyl fiber, silica fiber, boron nitride fiber, copper powder, iron powder, zinc powder, aluminum powder, lead powder, tin powder, talc, Inorganic fillers such as aluminum, mica, titanium oxide, iron oxide, and calcium carbonate can be added, and colorants, stabilizers, etc. can also be added as necessary.

<Examples and Comparative Examples> The present invention will be explained in more detail below according to Examples and Comparative Examples, but the scope of the present invention is not limited to these examples. In each example, "[part]" indicates the cliff area.

Example 1 N-methyl-
2914 parts of 2-pyrrolidone (hereinafter abbreviated as rNMPJ) (
50 mol) and 5 parts (1
, 0 mol) and N! The temperature was gradually raised while stirring under a gas stream. When the internal temperature reached approximately 150°C, water began to seep out from the distillation column, and heating was continued until the internal temperature reached 190°C. When 32.4 parts (1.8 mol) of water was leached out, a portion of VcNMP was also leached out. After cooling the internal temperature to 170°C, 146.47 parts (09964 mol) of p-dichlorobenzene (hereinafter abbreviated as rp-DCBJ) and 1.9
5 parts (10036 mol) of 2.4.4',4''-tetrabromo-m-terphenyl and 1s with N2
．． 5/- Closed after processing. Gradually raise the temperature to 250
After polymerization was carried out at ℃ for 3 hours, the autoclave was gradually cooled while stirring, and when the internal temperature reached room temperature, the autoclave was opened, the contents were poured into water, and the crystals were filtered. The obtained r-filter cake was washed repeatedly with water, then with acetone, and then dried at 80°C for 3 hours to obtain 101.4 parts of a grayish-white polymer.The yield was 9.
It was 5%. The melt viscosity of this polymer was measured with a high slag flow tester and was found to be s 180 PI.

Examples 2 to 5 Several types of branched phenylene sulfide polymers were produced in the same manner as in Example 1, except that the types of raw materials and the amounts used were changed. These raw materials and results are shown in Table 1 together with Example 1. In addition, "Te -BMTP' in Table 1 is 2
, 4.4', 4''-tetrap a A - m -tafeni k, @Te -BOTP'' is 4. s% a', a
ll-tetrapa and mu-terphenyl, respectively.

Comparative Example 1 Melt viscosity was measured under the same conditions as in Example 1 using PP8 commercial product Rydon v-1 (manufactured by PPS 1 Films Vetrolium Compagnie, which had not been heat-cured immediately after reaction) and found to be 12 Pas. It showed a low value.

Comparative Example 2 Baradichlorobenzene 146.12f (α994 mol)
For r, ter722lene boryhalide's blini L2+4- t131 o * benzene 1.09P
Branched phenylene sulfide was produced in the same manner as in Example 1 using (0,006 mol). Melt viscosity is 90P
The value was as low as am.

<Effects of the Invention> As can be seen from the above explanation, the branched phenylene sulfide polymer of the present invention is characterized by a significantly improved melt viscosity compared to commercially available PP8.

Hodogaya Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X, X', X'' are F, Cl, Br or I
Indicates atoms and may be the same or different from each other. l, m, n represent 0 or an integer of 1 to 3, l
+m+n=4 or 5) and dihalogenated benzene, the molar ratio of terphenylene polyhalide/dihalogenated benzene is in the range of 0.001 to 0.02. A method for producing a branched phenylene sulfide polymer, which comprises reacting the branched phenylene sulfide polymer with an alkali metal sulfide in an organic polar solvent.