To provide: a method of manufacturing granular polyarylene sulfide (PAS) with improved particle strength while improving the yield of the granular PAS by introducing and recovering PAS with a moderate molecular weight in granular PAS; and granular PAS.

A method of manufacturing granular PAS according to the present invention includes: a polymerizing step of subjecting a dihalo aromatic compound and at least one type of sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides to polymerization reaction in an organic amide solvent; and a cooling step of cooling the reaction product mixture after the polymerizing step. Addition of a phase separation agent to the reaction product mixture is started at a point in time from the start of the polymerizing step to before the start of forming granular PAS in the cooling step, and when the temperature of the reaction product mixture is 245 C. or higher, 50 mass % or greater of the phase separation agent is added to the reaction product mixture. The polymerizing step includes a predetermined PAS prepolymer generating step, and a predetermined converting step to a high molecular weight PAS.

A method for preparing a polyarylene sulfide includes reacting a methyl 4-(arylthio)aryl sulfoxide compound with sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid to obtain a polysulfonium intermediate; and demethylating the polysulfonium intermediate to obtain a polyarylene sulfide, wherein the polysulfonium intermediate is demethylated with aqueous HCl, HBr, or HI.

A method for preparing a polyarylene sulfide includes reacting a methyl 4-(arylthio)aryl sulfoxide compound with sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid to obtain a polysulfonium intermediate; and demethylating the polysulfonium intermediate to obtain a polyarylene sulfide, wherein the polysulfonium intermediate is demethylated with aqueous HCl, HBr, or HI.

Disclosed is a production method comprising a step of obtaining a poly(arylene sulfonium salt) comprising a terminal group including at least one functional group selected from the group consisting of a carboxy group, a hydroxy group and an amino group, and a step of dealkylating or dearylating the poly(arylene sulfonium salt) to obtain a polyarylene sulfide resin, and a polyarylene sulfide resin comprising a terminal group including a functional group obtainable by the production method.

Disclosed is a production method comprising a step of obtaining a poly(arylene sulfonium salt) comprising a terminal group including at least one functional group selected from the group consisting of a carboxy group, a hydroxy group and an amino group, and a step of dealkylating or dearylating the poly(arylene sulfonium salt) to obtain a polyarylene sulfide resin, and a polyarylene sulfide resin comprising a terminal group including a functional group obtainable by the production method.

A method for preparing a polyarylene sulfide includes reacting a methyl 4-(arylthio)aryl sulfoxide compound with sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid to obtain a polysulfonium intermediate; and demethylating the polysulfonium intermediate to obtain a polyarylene sulfide, wherein the polysulfonium intermediate is demethylated with aqueous HCl, HBr, or HI.

A method for preparing a polyarylene sulfide includes reacting a methyl 4-(arylthio)aryl sulfoxide compound with sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid to obtain a polysulfonium intermediate; and demethylating the polysulfonium intermediate to obtain a polyarylene sulfide, wherein the polysulfonium intermediate is demethylated with aqueous HCl, HBr, or HI.

A polymer is provided. The polymer has a repeating unit having a structure represented by Formula (I) or Formula (II)

##STR00001##

wherein Ar.sup.1 and Ar.sup.2 can be substituted or unsubstituted aryl diradical; Y.sup. can be R.sup.2SO.sub.3.sup. or ClO.sub.4.sup.; R.sup.1 can be C.sub.1-6 alkyl; Ar.sup.1 and Ar.sup.2 are different; and, R.sup.2 can be C.sub.1-6 alkyl, substituted or unsubstituted aromatic ring, or C.sub.1-6 haloalkyl.

A polymer is provided. The polymer has a repeating unit having a structure represented by Formula (I) or Formula (II)

##STR00001##

wherein Ar.sup.1 and Ar.sup.2 can be substituted or unsubstituted aryl diradical; Y.sup. can be R.sup.2SO.sub.3.sup. or ClO.sub.4.sup.; R.sup.1 can be C.sub.1-6 alkyl; Ar.sup.1 and Ar.sup.2 are different; and, R.sup.2 can be C.sub.1-6 alkyl, substituted or unsubstituted aromatic ring, or C.sub.1-6 haloalkyl.

Described herein are poly(arylene sulfide) (PAS) polymers (PASP) including recurring units formed from selected dihalofluorene monomers. Surprisingly, at relative low dihalofluorene monomer concentrations, the PAS polymers (PASP) have significantly increased glass transition temperatures (T.sub.g) and impact performance, relative to analogous PAS homopolymers and PAS polymers (PASP) including recurring units formed from 4,4-dibromobiphenyl (DBBP). Simultaneously, the PAS polymers (PASP) also retain high elastic modulus. Furthermore, the PAS polymers (PASP) are free of recurring units formed from polyhalogenated biphenyls (e.g. DBBP and polychlorinated biphenyls) and, therefore, are not currently subject to restrictive governmental regulation. Due at least in part to the excellent thermal (T.sub.g, T.sub.c and T.sub.m) and impact properties of the PAS polymers (PASP), the PAS polymers (PASP) and PAS polymer compositions can be desirably incorporated into wide variety of articles including, but not limited to, automotive articles, electrical and electronic articles, articles for aerospace and oil and gas articles.