Polyarylene sulfide resin composition and formed article

Abstract

The present invention relates to a polyarylene sulfide resin composition having good processability and showing excellent properties due to its more improved miscibility with other polymer materials or fillers, and a formed article. Such polyarylene sulfide resin composition includes a polyarylene sulfide including a disulfide repeating unit in the repeating units of the main chain; and at least one component selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, and a filler.

Claims

1. A polyarylene sulfide resin composition, including a polyarylene sulfide including a disulfide repeating unit in the repeating units of the main chain and having a target viscosity; and at least one component selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, and a filler, wherein the polyarylene sulfide includes carboxyl group (—COOH) bonded to at least part of end groups of the main chain, wherein the polyarylene sulfide is prepared by a method comprising the steps of: (a) melt-polymerizing a reactant comprising a diiodoaromatic compound and elemental sulfur while adding a polymerization inhibitor, and (b) adding a compound having a carboxyl group only when a degree of polymerization of the melt-polymerizing step as determined by a ratio of present viscosity to the target viscosity is at least about 90% to 95%; and wherein an FT-IR spectrum of the polyarylene sulfide shows a first peak between 1400 cm and 1600 cm.sup.−1 and a second peak between 1600 cm and 1800 cm.sup.−1, wherein a height intensity of the second peak is between about 0.5% and about 10% of a height intensity of the first peak.

2. The polyarylene sulfide resin composition according to claim 1, wherein the disulfide repeating unit is included in the amount of 3 weight % or less, based on the whole polyarylene sulfide.

3. A method of preparing a formed article, including the step of extruding the resin composition of claim 2.

4. A method of preparing a formed article, including the step of injection molding the resin composition of claim 2.

5. The method according to claim 4, wherein the injection molding is performed in a mold having a temperature of 50° C.

6. The polyarylene sulfide resin composition according to claim 1, wherein the thermoplastic resin is one or more selected from the group consisting of polyvinylalcohol-based resins, vinylchloride-based resins, polyamide-based resins, polyolefin-based resins, and polyester-based resins.

7. The polyarylene sulfide resin composition according to claim 1, wherein the thermoplastic elastomer is one or more selected from the group consisting of polyvinylchloride-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and polybutadiene-based elastomers.

8. The polyarylene sulfide resin composition according to claim 1, wherein the filler is a fiber type, a bead type, a flake type, or a powder type of organic or inorganic filler.

9. The polyarylene sulfide resin composition according to claim 1, wherein the filler is one or more selected from the group consisting of glass fiber, carbon fiber, boron fiber, glass bead, glass flake, talc, and calcium carbonate.

10. The polyarylene sulfide resin composition according to claim 1, wherein the number average molecular weight of the polyarylene sulfide is 5,000 to 50,000.

11. The polyarylene sulfide resin composition according to claim 1, including 5 to 95 weight % of the polyarylene sulfide and 5 to 95 weight % of one or more components selected from the group consisting of thermoplastic resins, thermoplastic elastomers, and fillers.

12. The polyarylene sulfide resin composition according to claim 1, further including an oxidation stabilizer, a photo stabilizer, a plasticizer, a lubricant, a nucleating agent, and an impact reinforcement.

13. A method of preparing a formed article, including the step of extruding the resin composition of claim 1.

14. The method according to claim 13, the extrusion is carried out with a twin screw extruder.

15. A formed article, including the polyarylene sulfide resin composition according to claim 1.

16. The formed article according to claim 15, which is a form of film, sheet, or fiber.

17. The formed article according to claim 15, which is used for car interior parts, car exterior parts, electric parts, electronic parts, or industrial materials.

18. A method of preparing a formed article, including the step of injection molding the resin composition of claim 1.

19. The method according to claim 18, wherein the injection molding is performed in a mold having a temperature of 50° C.

Description

DETAILED DESCRIPTION OF THE EMBODIMENT

(1) Hereinafter, preferable examples are presented for understanding the present invention. However, the following examples are only for illustrating the present invention and the present invention is not limited to or by them.

Example 1: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(2) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 51 g of 4-iodobenzoic acid thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(3) The polyarylene sulfide resin of Example 1 was analyzed by FT-IR spectroscopy. At this time, the carboxyl group peak was recognized at about 1600 to 1800 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 1600 to 1800 cm.sup.−1 was about 3.4% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 2: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(4) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 51 g of 4-iodoaniline thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(5) The polyarylene sulfide resin of Example 2 was analyzed by FT-IR spectroscopy. At this time, the amine group peak was recognized at about 3300 to 3500 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 3300 to 3500 cm.sup.−1 was about 1.4% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 3: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(6) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 25 g of 4-iodobenzoic acid thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(7) The polyarylene sulfide resin of Example 3 was analyzed by FT-IR spectroscopy. At this time, the carboxyl group peak was recognized at about 1600 to 1800 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 1600 to 1800 cm.sup.−1 was about 2.1% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 4: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(8) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 25 g of 4-iodoaniline thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(9) The polyarylene sulfide resin of Example 4 was analyzed by FT-IR spectroscopy. At this time, the amine group peak was recognized at about 3300 to 3500 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 3300 to 3500 cm.sup.−1 was about 1.1% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 5: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(10) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 51 g of 2,2′-dithiodibenzoic acid thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(11) The polyarylene sulfide resin of Example 5 was analyzed by FT-IR spectroscopy. At this time, the carboxyl group peak was recognized at about 1600 to 1800 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 1600 to 1800 cm.sup.−1 was about 3.2% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 6: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(12) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 51 g of 4,4′-dithiodianiline thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(13) The polyarylene sulfide resin of Example 6 was analyzed by FT-IR spectroscopy. At this time, the amine group peak was recognized at about 3300 to 3500 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 3300 to 3500 cm.sup.−1 was about 1.3% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 7: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(14) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 25 g of 2,2′-dithiodibenzoic acid thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(15) The polyarylene sulfide resin of Example 7 was analyzed by FT-IR spectroscopy. At this time, the carboxyl group peak was recognized at about 1600 to 1800 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 1600 to 1800 cm.sup.−1 was about 1.9% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 8: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(16) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto as a polymerization inhibitor and the reaction was carried out for 1 hr. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 25 g of 4,4′-dithiodianiline thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(17) The polyarylene sulfide resin of Example 8 was analyzed by FT-IR spectroscopy. At this time, the amine group peak was recognized at about 3300 to 3500 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 3300 to 3500 cm.sup.−1 was about 1.0% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 9: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(18) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto step by step, 5 g at a time, at intervals of 10 mins as a polymerization inhibitor and the reaction was carried out for 1 hr after the last inhibitor was added. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 25 g of 4-iodobenzoic acid thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(19) The polyarylene sulfide resin of Example 9 was analyzed by FT-IR spectroscopy. At this time, the carboxyl group peak was recognized at about 1600 to 1800 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 1600 to 1800 cm.sup.−1 was about 2.2% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Example 10: Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine Group at the End of the Main Chain

(20) After completely melting and mixing the reactant including 5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactor equipped with a thermocouple capable of measuring the inside temperature of the reactor and a vacuum line for nitrogen purging and vacuumizing by heating the same to 180° C., the polymerization reaction was proceeded by carrying out temperature-rising and pressure reducing step by step from the initial reaction condition of 220° C. and 350 torr to the final reaction temperature of 300° C. and the pressure of 1 torr or less. When the polymerization reaction was proceeded 80% (the proceeding degree of the polymerization reaction was identified by the relative viscosity ratio [(present viscosity/target viscosity)*100%], and the present viscosity was measured with a viscometer after taking a sample from the reactor where the polymerization reaction was progressing), 25 g of 2,2′-dithiobisbenzothiazole was added thereto step by step, 5 g at a time, at intervals of 10 mins as a polymerization inhibitor and the reaction was carried out for 1 hr after the last inhibitor was added. And then, sulfur was added thereto 3 times, 0.2 g at a time, at intervals of 1 hour in order to control the content of the disulfide. Subsequently, after adding 25 g of 4-iodoaniline thereto when the reaction was proceeded 90% and progressing the reaction under nitrogen circumstance for 10 mins, the reaction was further progressed with slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By this, the polyarylene sulfide resin having carboxyl group or amine group at the end of the main chain was synthesized. The final resin obtained by the reaction was prepared into pellets by using a small strand cutter.

(21) The polyarylene sulfide resin of Example 10 was analyzed by FT-IR spectroscopy. At this time, the amine group peak was recognized at about 3300 to 3500 cm.sup.−1 in the spectrum. It was also recognized that the relative height intensity of the peak at about 3300 to 3500 cm.sup.−1 was about 1.3% when the height intensity of the ring stretch peak shown at about 1400 to 1600 cm.sup.−1 was assumed as 100%.

Comparative Example 1

(22) The polyarylene sulfide (MV: 2,000 poise, Tm: 282° C.; Celanese) made by Macallum process was prepared.

Comparative Example 2

(23) The polyarylene sulfide (MV: 2,300 poise, Tm: 281° C.; Deyange) made by Macallum process by other company than Comparative Example 1 was prepared.

Comparative Example 3

(24) Product name Z200 of DIC Co., Ltd. in which the polyarylene sulfide made by Macallum process was compounded with an elastomer was used as Comparative Example 3.

Experimental Example 1: Evaluation on Basic Properties of Polyarylene Sulfide

(25) The properties of polyarylene sulfides of Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated by the following methods:

(26) Melting Temperature (Tm)

(27) By using a differential scanning calorimeter (DSC), after elevating the temperature of the specimen from 30° C. to 320° C. with a scanning speed of 10° C./min and cooling to 30° C., the melting temperature was measured while elevating the temperature from 30° C. to 320° C. again with a scanning speed of 10° C./min.

(28) Number Average Molecular Weight (Mn) and Polydispersity Index (PDI)

(29) After dissolving the polyarylene sulfide in 1-chloronaphthalene at 250° C. for 25 minutes with stirring so as to be 0.4 wt % solution, the polyarylene sulfide was divided in order in the column of a high temperature gel permeation chromatography (GPC) system (210° C.) by flowing the solution with the flow rate of 1 mL/min, and the intensity corresponding to the molecular weight of the divided polyarylene sulfide was measure by using a RI detector. After making a calibration line with a standard specimen (polystyrene) of which the molecular weight was known, the relative number average molecular weight (Mn) and polydispersity index (PDI) of the measure sample was calculated.

(30) Melt Viscosity (Poise)

(31) The melt viscosity (hereinafter, ‘W.V.’) was measured at 300° C. by using a rotating disk viscometer. In frequency sweep measuring method, angular frequency was measured from 0.6 to 500 rad/s, and the viscosity at 1.84 rad/s was defined as the melt viscosity (M.V.).

(32) Measurement on Flowability of Polymer

(33) A spiral test which has been generally used for measuring the flowability of polymerized polymer was used. For the following test, every polymerized specimen was cut into pellets having the diameter of 1˜2 mm and the length of 2˜4 mm during the polymer came out of the polymerization reactor. At this time, the maximum injection pressure in the injection machine, the injection charge, the ejection rate, the pressure of injection, and the holding pressure were uniformly regulated, and the injection temperature (based on barrel) was fixed to 320° C. After the spiral test, the final length of the formed article separated from the mold was measured, and the results are listed in Table 1.

(34) Measurement on Flashes Formed During the Preparation of Formed Article

(35) After spiral test was carried out by using the polymers of Comparative Examples and Examples, except the main shaped body corresponding to the mold which was used to the spiral test, the thin parts held between the front part and the back part of the mold were cut and weighed as flashes.

(36) The properties measured like above are listed in the following Table 1:

(37) TABLE-US-00001 TABLE 1 Melting temperature Number Average Polydispersity Melt Viscosity Flowability Amount of Flash Classification (° C.) Molecular Weight Index (PDI) (Poise) (cm) Generation (g) Example 1 278.6 17,667 2.9 2,940 48 0.01 Example 2 278.3 17,614 2.9 2,200 58 0.15 Example 3 278.8 17,435 2.8 2,830 50 0.04 Example 4 278.6 17,224 2.8 2,770 52 0.08 Example 5 277.5 17,338 2.9 2,350 58 0.12 Example 6 277.7 17,152 2.9 2,930 49 0.01 Example 7 278.3 17,531 2.8 2,470 57 0.15 Example 8 278.7 17,582 2.8 2,530 55 0.10 Example 9 279.1 17,884 2.8 2,450 58 0.08 Example 10 279.0 17,912 2.8 2,360 59 0.12 Comparative 282.0 15,237 3.1 2000 62 0.54 Example 1 Comparative 281.0 10,543 3.3 2300 57 0.42 Example 2

(38) Referring to Table 1, it is recognized that the polyarylene sulfides of Examples including the polyarylene disulfide repeating unit formed by adding sulfur during the preparation process show excellent processability when forming an article requiring high degree of precision because of their optimized flowability and small amount of flash generation. On the contrary, it is recognized that the polyarylene sulfides of Comparative Examples 1 and 2 show inferior processability to the polyarylene sulfides of Examples because of relatively large amount of flash generation.

Experimental Example 2: Evaluation on Mechanical Properties of Polyarylene Sulfide

(39) The mechanical properties of polyarylene sulfides of Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated by the following methods:

(40) Tensile Strength and Elongation

(41) The tensile strength and the elongation of the polyarylene sulfide specimens prepared according to Examples 1 to 10 and Comparative Examples 1 and 2 were measured according to ASTM D 638 method.

(42) Flexural Strength

(43) The flexural strength of the polyarylene sulfide specimens prepared according to Examples 1 to 10 and Comparative Examples 1 and 2 were measured according to ASTM D 790 method.

(44) Impact Strength (Izod)

(45) The impact strength of the polyarylene sulfide specimens prepared according to Examples 1 to 10 and Comparative Examples 1 and 2 was measured according to ASTM D 256 method.

(46) The mechanical properties measured according to above methods are listed in the following Table 2:

(47) TABLE-US-00002 TABLE 2 Tensile Flexural Strength Elongation Strength Impact Strength Classification (kgf/cm.sup.2) (%) (kgf/cm.sup.2) (J/m, Notched) Example 1 612 2.2 1,430 17 Example 2 602 1.2 1,422 20 Example 3 622 2.1 1,433 18 Example 4 614 1.3 1,442 17 Example 5 628 2.2 1,455 18 Example 6 605 1.2 1,428 17 Example 7 611 2.3 1,435 17 Example 8 618 1.3 1,447 19 Example 9 630 2.4 1,475 22 Example 10 625 1.5 1,465 20 Comparative 650 3.4 1,490 27 Example 1 Comparative 647 2.8 1,475 25 Example 2

(48) The specimens were prepared by compounding the polyarylene sulfide of Examples 1 to 8 and Comparative Example 1 with other components according to the following methods:

(49) Compounding of Polyarylene Sulfide and Glass Fiber (GF)

(50) After drying the polymerized resin, the compounding was carried out with a small twin-screw extruder under the condition of the extrusion die temperature of 300° C. and the screw speed of 200 rpm while adding 40 parts by weight of glass fiber to 60 parts by weight of the resin.

(51) Compounding of Polyarylene Sulfide and Elastomer

(52) The mixing extrusion was carried out under the condition of the extrusion die temperature of 300° C. and the screw speed of 200 rpm while adding 10 parts by weight of Lotader (Grade AX-8840, made by Arkema), the elastomer, to 90 parts by weight of the resin.

(53) The mechanical properties of the compounded specimens were evaluated by the same way as the polyarylene sulfide specimens and are listed in the following Table 3. Furthermore, such mechanical properties are listed together in the following Table 3 compared to the commercialized compounded specimen of Comparative Example 3:

(54) TABLE-US-00003 TABLE 3 Tensile Flexural Impact Strength Elongation Strength Strength Classification (kgf/cm.sup.2) (%) (kgf/cm.sup.2) (J/m, Notched) Example 1 + 583 25.2 1,030 54 Elastomer 10% Example 2 + 1,750 1.8 2,440 85 GF 40% Example 3 + 577 20.5 1,010 48 Elastomer 10% Example 4 + 1,740 1.8 2,400 83 GF 40% Example 5 + 564 24.3 1,010 52 Elastomer 10% Example 6 + 1,770 1.8 2,480 86 GF 40% Example 7 + 568 18.7 1,005 45 Elastomer 10% Example 8 + 1,750 1.8 2,420 82 GF 40% Example 9 + 603 27.5 1,130 60 Elastomer 10% Example 10 + 1,840 2.2 2,650 92 GF40% Comparative 660 15.7 940 76 Example 3 (Elastomer compounding)

(55) According to Tables 2 and 3, it was recognized that the elongation and the impact strength were largely increased by compounding the polyarylene sulfides of Examples 1 to 10 of which carboxyl group or amine group is introduce to the end of the main chain with the thermoplastic elastomer. And, it was recognized that the tensile strength was largely increased by compounding the polyarylene sulfides of Examples 1 to 10 with glass fiber. And, it was recognized that the elongation and the impact strength of the polyarylene sulfide of Example 9 prepared by adding the polymerization inhibitor step by step were largely improved by compounding the same with the thermoplastic elastomer. And, it was recognized that the tensile strength and the impact strength of the polyarylene sulfide of Example 10 were largely improved by compounding the same with the glass fiber. From the improvement of the properties caused by such compounding, it is recognized that the polyarylene sulfides of Examples can show excellent compatibility with various other polymer materials or fillers and thus the compounded resin composition can show excellent synergistic effect.

(56) On the other hand, it was recognized that the polyarylene sulfides of Comparative Examples were inferior in the compatibility with other polymer materials or fillers and the synergistic effects caused by compounding was not so big.