Branched polyarylene sulfide resin, method for manufacturing same and use as polymer modifier

Abstract

Disclosed is a branched polyarylene sulfide resin including an —S— substituent group with a cleaved disulfide compound which has a melt viscosity as measured at a halogen content of 4,000 ppm or less, a temperature of 330° C. and a shear rate of 2 sec −1 of 1.0×10 4 to 50.0×10 4 Pa·s and a melt viscoelasticity tan δ as measured at a temperature of 310° C. and an angular velocity of 1 rad/sec of 0.1 to 0.6.

1 . A branched polyarylene sulfide resin comprising an —S— substituent group with a cleaved disulfide compound, wherein the resin has the following characteristics i to iii:
 i) a halogen content of 4,000 ppm or less; 
 ii) a melt viscosity as measured at a temperature of 330° C. and a shear rate of 2 sec −1  of 1.0×10 4  to 50.0×10 4  Pa·s; and 
 iii) a melt viscoelasticity tan δ as measured at a temperature of 310° C. and an angular velocity of 1 rad/sec of 0.1 to 0.6. 
 
     
     
         2 . The branched polyarylene sulfide resin according to  claim 1 , wherein the halogen is chlorine. 
     
     
         3 . The branched polyarylene sulfide resin according to  claim 2 , wherein the chlorine content is 2,000 ppm or less. 
     
     
         4 . The branched polyarylene sulfide resin according to  claim 1 , wherein the disulfide compound is diphenyl disulfide. 
     
     
         5 . A method for manufacturing a branched polyarylene sulfide resin including an —S— substituent group with a cleaved disulfide compound that polymerizes a sulfur source with a dihalo aromatic compound in an organic amide solvent in the presence of a disulfide compound and a polyhalo aromatic compound having three or more halogen substituent groups in the molecule, the method comprising the steps of:
 performing a polymerization reaction of a sulfur source with a dihalo aromatic compound in an organic amide solvent using the dihalo aromatic compound in an amount of from 0.95 to 1.02 mol per mol of sulfur source; 
 adding a disulfide compound in an amount of from 0.001 to 0.03 mol per mol of sulfur source during the time interval between a stage when the conversion ratio of the dihalo aromatic compound is 0% and a stage when a polyhalo aromatic compound is added and reacting the mixture; 
 adding a polyhalo aromatic compound, in an amount of from 0.002 to 0.06 mol per mol of sulfur source and an amount of from 0.2 to 12 mol per mol of disulfide compound, to the polymerization reaction mixture at a stage when the conversion ratio of the dihalo aromatic compound reaches 80% or more; and 
 performing a phase separation polymerization reaction in the presence of a phase separation agent. 
 
     
     
         6 . The manufacturing method according to  claim 5 , further comprising the steps of:
 (1) heating a mixture containing an organic amide solvent, a sulfur source including an alkali metal hydrosulfide and an alkali metal hydroxide, and discharging at least part of the distillate containing water from the inside of the system containing the mixture to the outside of the system (dehydration step 1);   (2) mixing the mixture remaining inside the system in the dehydration step 1 with a dihalo aromatic compound to prepare a charged mixture containing an organic amide solvent, a sulfur source (hereinafter, referred to as “charged sulfur source”), an alkali metal hydroxide, water and a dihalo aromatic compound, wherein the amount of the dihalo aromatic compound in the charged mixture is from 0.95 to 1.02 mol per mol of charged sulfur source (charging step 2);   (3) heating the charged mixture to a temperature of from 170 to 270° C. and performing a polymerization reaction of the charged sulfur source and the dihalo aromatic compound in a water-containing organic amide solvent, adding a disulfide compound in an amount of from 0.001 to 0.03 mol per mol of charged sulfur source during the time interval between a stage when the conversion ratio of the dihalo aromatic compound is 0% and a stage when a polyhalo aromatic compound is added and reacting the mixture, adding a polyhalo aromatic compound (in an amount of from 0.002 to 0.06 mol per mol of charged sulfur source and an amount of from 0.2 to 12 mol per mol of disulfide compound) to the polymerization reaction mixture at a stage when the conversion ratio of the dihalo aromatic compound reaches 80% or greater and performing a polymerization reaction (prestage polymerization step 3); and   (4) heating the polymerization reaction mixture to a temperature of 240° C. or higher and performing a phase separation polymerization reaction at a temperature of from 240 to 290° C. in the presence of a phase separation agent (poststage polymerization step 4).   
     
     
         7 . The manufacturing method according to  claim 5 , wherein the total of the halogen content in the dihalo aromatic compound and the halogen content in the polyhalo aromatic compound is from 1.01 to 1.05 mol per mol of charged sulfur source. 
     
     
         8 . The manufacturing method according to  claim 6 , wherein when the conversion ratio of the dihalo aromatic compound in the prestage polymerization step 3 reaches 80% or greater, a phase separation agent is added. 
     
     
         9 . Use of the branched polyarylene sulfide resin according to  claim 1  as a polymer modifier. 
     
     
         10 . The use according to  claim 9 , wherein the use of the branched polyarylene sulfide resin as the polymer modifier is use as a burr suppressor with respect to a linear polyarylene sulfide resin.