JPH0820644A - High molecular weight polyarylene sulfide for blow-molding - Google Patents

Abstract

PURPOSE:To obtain the subject polymer reduced in the drawing-down of a parison on the blow-molding of the polymer, excellent in appearance and cost, and useful for medical care containers, etc., by adding a polyhalogenated aromatic compound, when an alkali metal sulfide is reacted with a dihalogenated aromatic compound. CONSTITUTION:This polymer is obtained by reacting (A) an alkali metal sulfide such as Li2S or Na2S with (B) a dihalogenated aromatic compound such as p-dichlorobenzene and (C) a polyhalogenated aromatic compound (e.g. 1,2,4- trichlorobenzene, 1,3,5-trichlorobenzene) in an amount of 0.2-1.0mol.% based on the component A in an organic amide solvent such as N-methylpyrrolidone or DMF, while the gaseous phase part of a reactor is cooled during the reaction to condense a part of the gaseous phase in the reactor and subsequently recycled to the liquid phase.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to high molecular weight polyarylene sulfides for blow molding and blow molded articles made therefrom.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter referred to as P
(Sometimes abbreviated as AS) has excellent resistance to acids, alkalis, various organic solvents and the like. Therefore, if it can be molded into a bottle, PAS is expected to be suitable for medical applications, food applications, and various chemical containers, such as bottles, tanks, and flasks.

However, when the PAS blow-molded article is molded by applying the blow-molding method commonly used for thermoplastic resins, PAS has the weakest melt tension required for blow-molding and the parison draws down. Therefore, it is extremely difficult to perform blow molding after that.

In view of such a current situation, Japanese Patent Laid-Open No. 61-25
No. 5832 discloses a melt viscosity of 3,000 to 20,000.
Disclosed is a PAS stretch blow molded container obtained by injection stretch blow molding a 0 poise substantially linear PAS. However, in the manufacturing method thereof, first, a bottomed parison is molded from the above PAS by injection molding, and then a rod is pushed through the opening of the bottomed parison to stretch in the longitudinal direction, and then a gas is blown into the parison. Since the operation procedure of stretching in the lateral direction is taken, there is a problem that the operation is complicated and the apparatus becomes expensive. The PAS used in this method is manufactured by the method described in JP-A No. 61-7332. That is, in the method for producing PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, in the first step, 0.5 to 2.4 mol of water is added per mol of the alkali metal sulfide. In the presence of the reaction, the reaction is carried out at a temperature of 180 to 235 ° C. to adjust the conversion of the dihaloaromatic compound to 50 to 98 mol%, and in the subsequent second step, water is added to add 2.5 to 7.0 mol of water. The reaction is further continued at a temperature of 245-290 ° C in the presence of. In this method, water must be added during the reaction. In order to do this, after the first step, the temperature is once lowered to normal pressure and then water is added, the reaction vessel is changed between the first step and the second step, or the reaction vessel under high temperature and high pressure is added. There is no choice but to press in water, which is economical,
Operationally disadvantageous. Also, in the second step, 2.5 mol or more of water is present per mol of sodium sulfide, and 245 ° C.
With the above temperature, the pressure becomes 20 kg / cm ² G or more. Therefore, the reaction can is actually 30 kg / cm ² G
The above pressure resistance is required, which is also disadvantageous in terms of equipment and economy.

Japanese Unexamined Patent Publication No. 3-247436 discloses a PA
Addition of 0.01 to 5 parts by weight of an alkoxysilane compound such as vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, allylalkoxysilane and mercaptoalkoxysilane to 100 parts by weight of S, and blow molding using melt-kneaded PAS. The method for producing a hollow molded article is described. However, the PAS melt tension was not sufficiently improved, and drawdown of the parison during blow molding could not be sufficiently suppressed.

JP-A-5-222196 discloses a method for producing PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, in which a gas phase portion of a reaction vessel is cooled. A part of the gas phase of the reaction vessel is condensed, refluxed in the liquid phase, and a polyhalo compound is used in a concentration of preferably 5 mol% or less with respect to p-dichlorobenzene to increase PAS to a high molecular weight. It is disclosed to obtain. In addition, the applicant of the present invention discloses that in order to obtain a high molecular weight PAS in Japanese Patent Application No. 4-331264, the polyhalo compound is added in an amount of 0.005 to 1.5 mol% based on the alkali metal sulfide in the above PAS production method. The invention has been filed for use in However, none of them describes that the produced PAS is remarkably suitable for blow molding.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an inexpensive high molecular weight polyarylene sulfide which gives a blow-molded article having a small drawdown of the parison during blow molding and good appearance characteristics.

[0008]

Means for Solving the Problems The present inventors have conducted extensive studies to solve the above-mentioned various drawbacks. As a result, when an alkali metal sulfide and a dihaloaromatic compound are reacted in an organic amide solvent and the gas phase portion of the reaction vessel is cooled during the reaction to produce a high molecular weight PAS, an amount within a predetermined range is obtained. By adding the polyhaloaromatic compound into the polymerization reaction system at 1, the drawdown of the parison at the time of PAS blow molding can be remarkably improved, and PA having excellent appearance characteristics can be obtained.
They have found that an S blow molded product can be obtained, and completed the present invention.

That is, according to the present invention, 0.2 to 1.0 mol% of a polyhaloaromatic compound is reacted with an alkali metal sulfide, a dihaloaromatic compound and a charged alkali metal sulfide in an organic amide solvent. , A high molecular weight polyarylene sulfide for blow molding, which is produced by cooling a gas phase part of a reaction can during the reaction to condense a part of the gas phase in the reaction can and refluxing it to a liquid phase. .

In the present invention, the amount of the alkali metal sulfide charged is 0.2 to 1.0 mol%, preferably 0.2 to 1.0 mol%.
0.6 mol% of polyhaloaromatic compound is added into the polymerization reaction system. By limiting the addition amount within the above range, it is possible to produce a blow-molded article having extremely excellent appearance characteristics. If the amount of the polyhaloaromatic compound added is less than the above lower limit, the drawdown of the parison during blow molding is not improved and the appearance properties are not improved. If the upper limit is exceeded, the melt viscosity of PAS becomes too high and blow molding becomes difficult, which is not preferable.

The method for adding the polyhaloaromatic compound into the polymerization reaction system is not particularly limited. For example, the alkali metal sulfide and the dihaloaromatic compound may be added at the same time, or the polyhaloaromatic compound may be dissolved in an organic solvent such as N-methylpyrrolidone at any time during the reaction, and the reaction vessel may be heated with a high pressure pump. You may press fit in.

The polyhaloaromatic compound is a compound having three or more halogen substituents in one molecule, for example, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5. -Trichlorobenzene, 1,
3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-
2,4,6-trimethylbenzene, 2,2 ', 4,4'
-Tetrachlorobiphenyl, 2,2 ', 6,6'-tetrabromo-3,3', 5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,
Examples thereof include 2,4-tribromo-6-methylnaphthalene and the like and mixtures thereof, with 1,2,4-trichlorobenzene and 1,3,5-trichlorobenzene being preferred.

As a method for producing PAS by condensing a part of the gas phase in the reaction vessel by cooling the gas phase portion of the reaction vessel of the present invention and then refluxing this to the liquid phase, Japanese Patent Laid-Open Publication No. Hei 5 (1998)
The method described in JP-A-222196 can be used.

The refluxed liquid has a high water content compared to the liquid phase bulk because of the vapor pressure difference between water and the amide solvent.
This reflux liquid having a high water content forms a layer having a high water content on the reaction solution. As a result, the residual alkali metal sulfide (for example, Na ₂ S), alkali metal halide (for example, NaCl), oligomer and the like are contained in a large amount in the layer. In the conventional method, at a high temperature of 230 ° C. or higher, when the generated PAS and the raw materials such as Na ₂ S and by-products are uniformly mixed, not only high-molecular-weight PAS cannot be obtained but Depolymerization of PAS also occurred, and thiophenol by-product was observed. However, in the present invention, by positively cooling the gas phase portion of the reaction vessel and returning a large amount of water-rich reflux liquid to the upper portion of the liquid phase, the above-mentioned inconvenient phenomenon can be avoided and the reaction is inhibited. Of high molecular weight PA
It seems that S can be obtained. However, the present invention is not limited only to the effects due to the above-mentioned phenomenon, and high-molecular weight PAS can be obtained by various influences caused by cooling the gas phase portion.

In the present invention, it is not necessary to add water during the reaction unlike the conventional method. However, the addition of water is not excluded at all. However, some of the advantages of the present invention are lost if the operation of adding water is performed. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The gas phase portion of the reaction can can be cooled by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a cooling medium into an internal coil installed in the upper part of the reaction can, a method of flowing a cooling medium into an external coil or jacket wound around the upper part of the outside of the reaction can, and a reflux condenser installed in the upper part of the reaction can are used. The method may be such as sprinkling water or blowing gas (air, nitrogen, etc.) on the upper part of the outside of the reaction can. Any method is effective as long as it has the effect of increasing the reflux amount in the can. May be used. If the outside air temperature is relatively low (for example, room temperature), it is also possible to perform appropriate cooling by removing the heat insulating material conventionally provided on the upper part of the reaction can. In the case of external cooling, water condensed on the reactor wall surface
The amide-based solvent mixture enters the liquid phase along the wall of the reaction vessel. Thus, the water-rich mixture pools on top of the liquid phase,
Keep the water content there relatively high. For internal cooling,
The mixture condensed on the cooling surface likewise travels along the surface of the cooling device or the wall of the reaction vessel into the liquid phase.

On the other hand, the temperature of the liquid phase bulk is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230 to 275 for constant temperature
It is preferable to carry out the reaction at a temperature of ° C for 0.1 to 20 hours. More preferably, the temperature is 240 to 265 ° C. and the time is 1 to 6 hours. To obtain higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. This 2
When carrying out the stepwise operation, the first step is preferably carried out at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too slow, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too fast, PAS having a sufficiently high molecular weight cannot be obtained, and the side reaction rate remarkably increases. The end of the first stage is
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out at a time of mol% and a molecular weight in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo-aromatic compound in the polymerization reaction system is 2 mol% to 15 mol% and the molecular weight is 5,000 to 15,000. Residual rate is 40 mol%
When it is more than 1, the side reaction such as depolymerization is likely to occur in the second step reaction, while when it is less than 1 mol%, the high molecular weight P is finally obtained.
It is difficult to get AS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. PAS with sufficiently high molecular weight at low temperature
At a temperature higher than 270 ° C., side reactions such as depolymerization are likely to occur, making it difficult to stably obtain a high molecular weight product.

As a practical operation, first, dehydration or water addition is carried out in an inert gas atmosphere so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount, if necessary. The water content is preferably alkali metal sulfide 1
The amount is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol per mol. If it exceeds 2.5 mols, the reaction rate will be low, and the amount of by-products such as phenol will increase in the filtrate after the reaction and the degree of polymerization will not increase. If it is less than 0.5 mol, the reaction rate will be too fast to obtain a sufficiently high molecular weight product.

In the case of the one-step reaction at a constant temperature, the cooling of the gas phase portion during the reaction is preferably performed from the start of the reaction, but it must be performed at least during the temperature increase of 250 ° C. or less. In the multi-stage reaction, it is preferable to perform cooling from the first-stage reaction, but it is preferable to perform cooling at the latest after the completion of the first-stage reaction. Regarding the degree of cooling effect, the pressure inside the reaction vessel is usually the most suitable index. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the water content in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, as compared with the case of not cooling under the same reaction conditions, if the reactor pressure is decreased, the amount of reflux liquid is increased, which means that the temperature at the reaction solution gas-liquid interface is decreased. It is considered that the degree of relative decrease indicates the degree of separation between the layer having a high water content and the layer having no water content. Therefore, it is preferable to cool the reactor so that the internal pressure of the reactor becomes lower than that in the case where no cooling is performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment used, operating conditions, and the like.

The organic amide solvent used here is PA
Known for S polymerization, for example N-methylpyrrolidone (NMP), N, N-dimethylformamide,
N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with NMP being preferred. They all have a lower vapor pressure than water.

Alkali metal sulphides are also known, for example lithium sulphide, sodium sulphide, potassium sulphide, rubidium sulphide, cesium sulphide and mixtures thereof. These hydrates and aqueous solutions may be used. Further, hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides.
Inexpensive sodium sulfide is preferred.

The dihalo aromatic compound is, for example, Japanese Patent Publication No.
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using a small amount (20 mol% or less) of one or more kinds of para, meta or orthodihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl. For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'-dichlorodiphenyl sulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
It is dichlorobiphenyl.

Further, as a small amount of other additives, a terminal terminating agent and a monohalo compound as a modifying agent can be used in combination.

The high molecular weight PAS thus obtained is separated from by-products by post-treatment methods known to those skilled in the art.

The high molecular weight PAS for blow molding produced as described above has a melt viscosity V ₆ of preferably 25,000 to 60,000 poises, particularly preferably 3
It is 50,000 to 50,000 poise. If the melt viscosity is less than the above lower limit, the drawdown of the parison during blow molding is not improved and the appearance characteristics of the blow molded product are not improved.
Exceeding the above upper limit is not preferable because the melt tension becomes too high and blow molding becomes difficult. Where melt viscosity V
₆ is 320 ℃ using a flow tester, load 20kg
Viscosity (poise) measured after holding at f / cm ² and L / D = 10 for 6 minutes.

Conventional additives may be added to the high molecular weight PAS for blow molding. For example, silica as an inorganic filler, alumina, talc, mica, kaolin, clay, silica-alumina, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium carbonate, magnesium oxide, magnesium phosphate, silicon nitride, Granular, powdery or scaly ones such as glass, hydrotalcite and zirconium oxide, or fibrous ones such as glass fibers, potassium titanate fibers, carbon fibers and mica ceramic fibers can be blended. These inorganic fillers can be used alone or in combination of two or more. Also,
These inorganic fillers may be treated with a silane coupling agent or a titanate coupling agent. From the viewpoint of melt processability, the blending ratio of the filler is preferably 30% by weight or less in the blow molded product.

Further, if necessary, additives such as an antioxidant, a heat stabilizer, a lubricant, a release agent and a coloring agent may be added.

The method of mixing the above components is not particularly limited. A generally widely used method, for example, a method of mixing each component with a mixer such as a Henschel mixer can be used.

The blow-molded article of the present invention is manufactured by a known method using a blow-molding machine generally used for blow-molding a thermoplastic resin. That is, the above PAS is plasticized by an extruder or the like, and this is extruded or injected by an annular die to form an annular molten or softened intermediate parison, and gas is blown into the parison in the mold, It is inflated and solidified by cooling to obtain a hollow body. PA
As the molding conditions for S, the cylinder and die temperatures are preferably 280 to 350 ° C., and particularly preferably 290 to 320.
° C. The mold temperature is preferably 40 to 200 ° C, particularly preferably 80 to 150 ° C. The gas blown into the interior may be air, nitrogen or the like, but air is generally used in consideration of economy. The blowing pressure is preferably 4 to 10 kg / cm ² .

The blow-molded article of the present invention can be used for medical applications, food applications, or containers for various chemicals such as bottles, tanks, flasks and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0032]

EXAMPLES In Examples, the melt viscosity V of polyphenylene sulfide (hereinafter sometimes abbreviated as PPS)
₆ is a Shimadzu CFT-500C flow tester at 320 ° C., load 20 kgf / cm ² , L / D = 1.
Viscosity (poise) measured after holding at 0 for 6 minutes.

P-dichlorobenzene (hereinafter p-DC
The reaction rate of (abbreviated as B) was calculated from the measurement result by gas chromatography. Here, the reaction rate of p-DCB was calculated by the following formula. Reaction rate (%) of p-DCB = (1-weight of residual p-DCB / weight of charged p-DCB) x 100

[0034]

Polymerization Example 1 Flake sodium sulfide (60.4 wt% Na ₂ S) was added to a 150 liter autoclave.
906 kg and 45.0 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. and water 4.9
1 kg was distilled. Then, the autoclave was closed and cooled to 180 ° C, p-DCB21.940kg,
1,2,4-trichlorobenzene (below 1,2,4
-TCB) 69.0 g (about 0.26 mol% with respect to sodium sulfide) and NMP 18.0 kg were charged. 1 kg / c at a liquid temperature of 150 ° C using nitrogen gas
Pressurization to m ² G was started to raise the temperature. While stirring at a liquid temperature of 220 ° C. for 5 hours, the upper portion of the autoclave was cooled by sprinkling water. After that, the temperature was raised and the liquid temperature was stirred at 260 ° C. for 5 hours, then the temperature was lowered and the cooling of the upper part of the autoclave was stopped. During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction is 8.
It was 59 kg / cm ² G. The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried at 120 ° C. for about 8 hours in a hot air circulation dryer to obtain a white powdery product. The melt viscosity V ₆ of the obtained PPS (P-1) is 28,600.
Poise.

The reaction rate of p-DCB is 99.2%.
Met.

[0036]

Polymerization Example 2 The addition amount of 1,2,4-TCB was 14
Polymerization Example 1 was repeated except that the amount was 6.0 g (0.55 mol% based on sodium sulfide).

Melt viscosity V _{6 of the} obtained PPS (P-2)
Was 44,700 poise.

The reaction rate of p-DCB is 98.7%.
Met.

[0039]

Polymerization Example 3 Sodium sulfide and p-DCB were added at a liquid temperature of 220.
Polymerization Example 1 was repeated except that 1,2,4-TCB was added after stirring for 4 hours at 0 ° C. The above addition is
Pre-dissolved 1,2,4-TCB 69.0 g in NMP 500 g was press-fitted into a reaction can with a small high pressure pump,
Then, it was performed by further press-fitting 500 g of NMP. The melt viscosity V ₆ of the obtained PPS (P-3) is 26,
It was 100 poise.

The reaction rate of p-DCB is 99.3%.
Met.

[0041]

Polymerization Example 4 Instead of 1,2,4-TCB, 1,
Polymerization Example 1 was repeated except that 3,5-trichlorobenzene was used.

Melt viscosity V _{6 of the} obtained PPS (P-4)
Was 42,600 poise.

The reaction rate of p-DCB is 99.2%.
Met.

[0044]

Polymerization Comparative Example 1 Polymerization Example 1 was repeated except that 1,2,4-TCB was not added. The obtained PPS
The melt viscosity V ₆ of (P-C1) was 1,350 poise.

The reaction rate of p-DCB is 99.1%.
Met.

[0046]

Polymerization Comparative Example 2 The addition amount of 1,2,4-TCB was 37.
Polymerization Example 1 was repeated except that the amount was 2 g (about 0.14 mol% based on sodium sulfide).

Melt viscosity V of the obtained PPS (P-C2)
₆ was 3,360 poise.

The reaction rate of p-DCB is 99.4%.
Met.

[0049]

[Polymerization Comparative Example 3] The addition amount of 1,2,4-TCB was 27
Polymerization Example 1 was repeated except that the amount was 8.1 g (about 1.07 mol% based on sodium sulfide).

The obtained PPS (P-C3) contained a gel. Melt viscosity V of PPS from which the gel is removed
₆ was 92,000 poise.

The reaction rate of p-DCB is 99.6%.
Met.

[0052]

Polymerization Comparative Example 4 Polymerization Example 1 was repeated except that water was not sprayed on the upper part of the autoclave and the addition amount of 1,2,4-TCB was 411.5 g (1.55 mol% based on sodium sulfide). I went the same. Maximum pressure during reaction is 10.25k
It was g / cm ² G.

The obtained PPS (P-C4) contained a gel. Melt viscosity V of PPS from which the gel is removed
₆ was 41,700 poise.

The reaction rate of p-DCB is 98.3%.
Met.

[0055]

Examples 1 to 4 and Comparative Examples 1 to 4 PPS obtained as described above was melted using a twin-screw extruder having a cylinder temperature of 320 ° C. to prepare pellets. Further, the obtained pellets are supplied to a blow molding machine, the cylinder temperature is 320 ° C., the die diameter is 55 mmφ, the mold temperature is
At 0 ° C, air blowing pressure 6 kg / cm ² , average thickness 2.4
A cylindrical container having a size of 500 mm and an internal volume of 500 cc was formed. At this time, the following evaluation was carried out. <Drawdown of parison> The drawdown of the parison at the time of blow molding was performed by extruding the parison to a length of 200 mm and measuring the length of the parison after 10 seconds, and evaluated as large, medium or small as follows. -Large: more than 250 mm-Medium: 210-250 mm-Small: less than 210 mm <Appearance characteristics> The appearance characteristics of the molded cylindrical container were evaluated according to the following criteria. -Good: The surface smoothness was visually inspected and judged to be smooth, and the cylindrical container was not torn.-Yes: Same as the above, it was judged to be uneven, and the cylindrical container was torn. No defect ・ Poor: There was breakage in the cylindrical container. The above results are shown in Table 1.

[0056]

[Table 1] Example 1 is 1,2,4 as a polyhalo aromatic compound.
-TCB was added within the scope of the present invention. The drawdown of the parison was relatively small, and it was possible to obtain a blow-molded product with good appearance characteristics. Example 2 has a larger amount of polyhaloaromatic compound added than Example 1. Increasing the amount of polyhaloaromatic compound added within the scope of the present invention further reduces the drawdown of the parison. The blow molded product had good appearance characteristics. Example 3 was carried out under the same conditions as Example 1, except that the polyhaloaromatic compound was added during the reaction. As in Example 1, the drawdown of the parison was relatively small, and a blow-molded product with good appearance characteristics could be obtained. Example 4, under the same conditions as Example 1, 1, 2, 4-
The TCB is replaced with 1,3,5-TCB. The drawdown of the parison was smaller, and it was possible to obtain a blow molded product with good appearance characteristics.

On the other hand, Comparative Example 1 was carried out under the same conditions as in Example 1 except that the polyhaloaromatic compound was not added. The melt viscosity of the produced PPS is extremely small,
The parison could not be molded due to resin breakage due to its own weight and could not be used for blow molding. Comparative Example 2 was carried out under the same conditions as in Example 1, except that the amount of polyhaloaromatic compound added was less than the lower limit of the range of the present invention.
The parison had a large drawdown and the blow molded product had poor appearance characteristics. Comparative Example 3 was carried out under the same conditions as in Example 1 except that the polyhaloaromatic compound was added above the upper limit of the range of the present invention. The melt viscosity of the produced PPS was extremely high, PPS could not be extruded, and it could not be used for blow molding. In Comparative Example 4, the polyhaloaromatic compound was added in excess of the upper limit of the range of the present invention, and the gas phase portion of the autoclave was not cooled. Compared to Example 1, the drawdown of the parison was small because the melt viscosity of the produced PPS was high, but the appearance characteristics of the molded product were remarkably poor.

[0058]

INDUSTRIAL APPLICABILITY The present invention provides an inexpensive high molecular weight polyarylene sulfide which has a small drawdown of the parison during blow molding and gives a blow molded article having good appearance characteristics.

Claims (4)

[Claims] 1. A reaction of 0.2 to 1.0 mol% of a polyhaloaromatic compound with respect to an alkali metal sulfide, a dihaloaromatic compound and a charged alkali metal sulfide in an organic amide solvent, and during the reaction. A high-molecular-weight polyarylene sulfide for blow molding, which is produced by cooling part of the gas phase of the reaction can to condense a part of the gas phase in the reaction can, and refluxing this to the liquid phase. 2. The amount of the alkali metal sulfide charged is 0.2.
The high molecular weight polyarylene sulfide for blow molding according to claim 1, which is reacted with ˜0.6 mol% of a polyhaloaromatic compound. 3. A melt viscosity V ₆ of 25,000 to 60,0.
The high molecular weight polyarylene sulfide for blow molding according to claim 1 or 2, which has a poise of 00. 4. A blow-molded article produced from the high-molecular-weight polyarylene sulfide for blow molding according to claim 1.