Patent Description:
The invention relates to poly(arylene sulfide) ("PAS") polymers having outstanding thermal properties and mechanical properties. The invention also relates to PAS polymer compositions, methods of making PAS polymers and PAS compositions and articles incorporating the PAS polymer and PAS polymer compositions.

While poly(arylene sulfide) ("PAS") polymers generally have high chemical resistance and desirable mechanical properties, they also have a relatively low Tg, (typically from <NUM> - <NUM>), which limits their use in some applications (e.g. thermoplastic composites), and low toughness (impact strength).

Known methods for increasing the Tg and toughness of PAS polymers involve forming polymer compositions including additives (e.g., tougheners) and incorporating a rigid comonomer such as <NUM>,<NUM>'-dibromobiphenyl ("DBBP") into the PAS polymer. With respect to polymer compositions, while tougheners increase the toughness of PAS polymers, they also dramatically reduce the elastic modulus (for example, usually below <NUM> GPa). With respect to DBBP, relatively high concentrations are required to obtain a Tg of greater than <NUM>, but in such cases the melting temperature is also very high (greater than <NUM>), which makes processing extremely difficult. Furthermore, DBBP is a polybrominated biphenyl ("PBB"), which belongs to a class of compounds (polyhalogenated biphenyls) that are heavily regulated. For example, DBBP is subject to US Environmental Protection Agency regulations under the Toxic Substances Control Act ("TSCA"). Accordingly, use of DBBP monomers is all but impossible under the current regulatory scheme.

<CIT> discloses optical materials comprising an aromatic sulfide compound represented by the formula (<NUM>): A-(- S - Bk)n, wherein n stands for an integer of from <NUM> to <NUM>, k stands for an integer of from <NUM> to n, A represents a substituted or unsubstituted, n-valent carbocyclic aromatic ring or heterocyclic aromatic ring, and B independently represent a substituted or unsubstituted, carbocyclic aromatic group or heterocyclic aromatic group. The optical materials are not polymeric materials.

<CIT> discloses a method of producing a PAS in which a dihalo aromatic sulfide compound represented by the formula: X-(-Ar-S-)n-Ar-X (in the formula, Ar represents an optionally substituted aromatic group, X represents a halogen atom, and n is from <NUM> to <NUM>) and a sulfur source containing an alkali metal are polymerized in an organic amide solvent.

<NPL>) discloses intra- versus inter-molecular electron transfer in radical nucleophilic aromatic substitution of dihalo(hetero)arenes as a tool for estimating [pi]-conjugation in aromatic systems.

<CIT> discloses bis(sulfonyl)biaryl compounds that are useful as electron transporting materials useful for making novel organic electronic devices, including the electron transport layers of organic light-emitting diodes ("OLEDs"), or as an electron transporting guest for phosphorescent guests in the emissive layer of OLEDs.

In one aspect, the invention relates to a poly(arylene sulfide) ("PAS") polymer (PASP) includes recurring units RPAS1 and RPAS2, represented by the following formulae, respectively:.

In some embodiments, -Ar<NUM>- is a diradical of a dihalofluorene monomer selected from the group consisting of <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dimethyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dipropyl-<NUM>-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dihexyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dioctyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-didodecyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-di-(<NUM>-ethylhexyl)-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-diphenyl-<NUM>H-fluorene; and <NUM>,<NUM>-dibromo-<NUM>,<NUM>-difluoro-<NUM>H-fluorene.

In some embodiments, the PAS polymer (PASP) has a Tg of at least <NUM>° C. Additionally or alternatively, in some embodiments, the PAS polymer (PASP) has a Tm of at least <NUM>. In still further additional or alternative embodiments, the PAS polymer (PASP) has an impact strength at least <NUM> J/g, as determined according to ASTM D256.

In another aspect, the invention relates to a polymer composition (PC) including the PAS polymer (PASP) and a toughener, a glass fiber, or both.

In a further aspect, the invention relates to an automotive component, an oil and gas component, or an aerospace component including the PAS polymer (PASP) or the polymer composition (PC).

In another aspect, the invention relates to a method of making the PAS polymer (PASP), the method including reacting in a reaction mixture a dihaloaromatic compound having the following formula: X<NUM>-Ar<NUM>-X<NUM>; a dihalofluorene monomer having the following formula: X<NUM>-Ar<NUM>-X<NUM>; and a sulfur compound, wherein X<NUM> to X<NUM> are independently selected halogens, and the sulfur compound is selected from the group consisting of thiosulfates, thioureas, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and bisulfides, and hydrogen sulfide; preferably the sulfur compound is an alkali metal sulfide; most preferably the sulfur compound is Na<NUM>S.

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 ("Tg") and impact performance, relative to analogous PAS homopolymers and PAS polymers (PASP) including recurring units formed from <NUM>,<NUM>'-dibromobiphenyl ("DBBP"). Simultaneously, the PAS polymers (PASP) also retain high elastic modulus (also referred to herein as modulus or Young's 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 (Tg, Tc and Tm) 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.

As used herein, "free of" a given recurring unit means that the concentration of the given recurring unit in the PAS polymer (PASP) is less than <NUM> mol%, preferably less than <NUM> mol%, more preferably less than <NUM> mol%, still more prefereably less than <NUM> mol%, even more preferably less than <NUM> mol%, and most preferably, <NUM> mol% (undetectable).

In the present application, any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Furthermore, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components; any element or component recited in a list of elements or components may be omitted from such list. Additionally, any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range.

Unless specifically limited otherwise, the term "alkyl", as well as derivative terms such as "alkoxy", "acyl" and "alkylthio", as used herein, include within their scope straight chain, branched chain and cyclic moieties. Examples of alkyl groups are methyl, ethyl, <NUM>-methylethyl, propyl, <NUM>,<NUM>-dimethylethyl, and cyclo-propyl. Unless specifically stated otherwise, each alkyl and aryl group may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, amino, hydroxy, sulfo, C<NUM>-C<NUM> alkoxy, C<NUM>-C<NUM> alkylthio, C<NUM>-C<NUM> acyl, formyl, cyano, C<NUM>-C<NUM> aryloxy or C<NUM>-C<NUM> aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine.

The term "aryl" refers to a phenyl, indanyl or naphthyl group. The aryl group may comprise one or more alkyl groups, and are called sometimes in this case "alkylaryl"; for example may be composed of an aromatic group and two C<NUM>-C<NUM> groups (e.g. methyl or ethyl). The aryl group may also comprise one or more heteroatoms, e.g. N, O or S, and are called sometimes in this case "heteroaryl" group; these heteroaromatic rings may be fused to other aromatic systems. Such heteroaromatic rings include, but are not limited to furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl and triazinyl ring structures. The aryl or heteroaryl substituents may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, C<NUM>-C<NUM> alkoxy, sulfo, C<NUM>-C<NUM> alkylthio, C<NUM>-C<NUM> acyl, formyl, cyano, C<NUM>-C<NUM> aryloxy or C<NUM>-C<NUM> aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.

The PAS polymer (PASP) includes recurring unit (RPAS1) and recurring unit (RPAS2) represented by the following formulae, respectively:.

In preferred embodiments, i and j, at each instance, is zero. Preferably, -Ar<NUM>-is represented by either Formula (<NUM>) or (<NUM>), more preferably Formula (<NUM>) ([-Ar<NUM>-S-] corresponding to recurring units of polyphenylene sulfide), still more preferably, -Ar<NUM>- is represented by the following formula:
<CHM>
Most preferably, -Ar<NUM>- is represented by Formula (<NUM>), where i is zero.

As demonstrated in the examples below, high molecular weight PAS polymer cannot be formed if R<NUM> and R<NUM> are both hydrogen. In some embodiments, R<NUM> and R<NUM> are independently selected from the group consisting of a C<NUM>-C<NUM> alkyl group, a C<NUM>-C<NUM> alkyaryl group, and a C<NUM>-C<NUM> aryl group. In some such embodiments, R<NUM> is a C<NUM>-C<NUM> alkyl group or R<NUM> is a C<NUM>-C<NUM> alkyl group; more preferably both R<NUM> and R<NUM> are C<NUM>-C<NUM> alkyl groups; most preferably, R<NUM> and R<NUM> are -CH<NUM> groups. In some embodiments, R<NUM> is a hydrogen and R<NUM> is selected from the group consisting of a C<NUM>-C<NUM> alkyl group, a C<NUM>-C<NUM> alkyaryl group, and a C<NUM>-C<NUM> aryl group. In some such embodiments, R<NUM> is a C<NUM>-C<NUM> alkyl group, preferably a -CH<NUM> group.

In some embodiments, -Ar<NUM>- is represented by the following formula:
<CHM>
In some such embodiments, k, at each location is zero. Additionally or alternatively, in some embodiments, R<NUM> is a C<NUM>-C<NUM> alkyl group, R<NUM> is a C<NUM>-C<NUM> alkyl group, or both R<NUM> and R<NUM> are C<NUM>-C<NUM> alkyl groups. Preferably R<NUM> is-CH<NUM>, R<NUM> is-CH<NUM> or R<NUM> and R<NUM> are both -CH<NUM>. In some embodiments, -Ar<NUM>- is a diradical of a dihalofluorene monomer selected from the group consisting of <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dimethyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dipropyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dihexyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dioctyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-didodecyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-di-(<NUM>-ethylhexyl)-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-diphenyl-<NUM>H-fluorene; and <NUM>,<NUM>-dibromo-<NUM>,<NUM>-difluoro-<NUM>H-fluorene. For clarity, a diradical of a dihalofluorene monomer refers to the diradical formed from dehalogenation of the explicit halogens in the dihalofluorene monomer (X<NUM> and X<NUM> in reaction scheme (S1), below). For example, the diradical of the dihalofluorene monomer <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dimethyl-<NUM>H-fluorene refers to the diradical formed from debromination of the <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dimethyl-<NUM>H-fluorene. In some embodiments, -Ar<NUM>- is represented by Formula (<NUM>), with i equal to zero, and -Ar<NUM>- is a diradical of a dihalofluorene monomer selected from the aforementioned group of dihalofluorene monmers. In one such embodiment, -Ar<NUM>- is a diradical of <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dimethyl-<NUM>H-fluorene.

In alternate embodiments, -Ar<NUM>- is represented by a formula selected from the group of formulae (<NUM>) to (<NUM>) and -Ar<NUM>- is a diradical of a spirobifluorene. In some such embodiments, the spirobifluorene is a <NUM>,<NUM>-dihalo-<NUM>,<NUM>-spirobifluorene or a <NUM>,<NUM>,<NUM>,<NUM>-tetrahalo-<NUM>,<NUM>-spirobifluorene, preferably <NUM>,<NUM>-dibromo-<NUM>,<NUM>-spirobifluorene or <NUM>,<NUM>,<NUM>,<NUM>-tetrabromo-<NUM>,<NUM>-spirobifluorene. In one such embodiment, -Ar<NUM>- is represented by formula (<NUM>), where i is zero.

In some embodiments, the total concentration of recurring units (RPAS1) and (RPAS2) in the PAS polymer is at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol% or at least <NUM> mol%,. As used herein, the molar concentration of recurring units in a polymer is relative to the total number of recurring units in that polymer, unless explicitly stated otherwise. In some embodiments, the concentration of recurring unit (RPAS1) is at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, or at least <NUM> mol%.

As noted above, it was surprisingly found that at relatively low concentration of recurring unit (RPAS2), the PAS polymers (PASP) had significantly increased Tg while maintaining or improving the toughness. In some embodiments, the concentration of recurring unit (RPAS2) is at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol% or at least <NUM> mol%. In some embodiments, the concentration of recurring unit (RPAS2) is no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol%, or no more than <NUM> mol%. In some embodiments, the number of moles of recurring unit (RPAS2) is from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol% or from <NUM> mol% to <NUM> mol%. In some embodiments, the ratio of the number of recurring unit (RPAS2) to the total number of recurring units (RPAS1) and (RPAS2) is at least <NUM> mol%, at least <NUM> mol%, at least <NUM> mol% or at least <NUM> mol%. In some embodiments, the ratio of the number of recurring unit (RPAS2) to the total number of recurring units (RPAS1) and (RPAS2) is no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol%, or no more than <NUM> mol%. In some embodiments, the ratio of the number of recurring unit (RPAS2) to the total number of moles of recurring units (RPAS1) and (RPAS2) is from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol%, from <NUM> mol% to <NUM> mol% or from <NUM> mol% to <NUM> mol%. Nevertheless, in some embodiments, the PAS polymer (PASP) has higher concentrations of recurring unit (RPAS2). In some such embodiments, the concentration of recurring unit (RPAS2) is from <NUM> mol% to no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol%, no more than <NUM> mol% or no more than <NUM> mol%.

Of course, in some embodiments, the PAS polymer can have additional recurring units, each distinct from each other and distinct from recurring units (RPAS1) and (RPAS2). In one such embodiment, the PAS polymer includes one or more additional recurring units according to Formula (<NUM>) or one or more additional recurring units according to Formula (<NUM>). In some embodiments including additional recurring units according to Formulae (<NUM>) and (<NUM>), the total concentration of recurring units according to Formulae (<NUM>) and (<NUM>) is within the ranges given above for recurring units (RPAS1) and (RPAS2), and the ratio of the total number of recurring units according to Formula (<NUM>) to the total number of recurring units according to Formulae (<NUM>) and (<NUM>) are within the ranges above given for recurring units (RPAS1) and (RPAS2). Of course in other embodiments, the concentration of the additional recurring units according to Formulae (<NUM>) and (<NUM>), as well as the number of additional recurring units according to Formula (<NUM>) to the total number of recurring units according to Formulae (<NUM>) and (<NUM>), is distinct from the ranges above given for recurring units (RPAS1) and (RPAS2).

In some embodiments, the PAS polymer has a weight average molecular weight ("Mw") of at least <NUM>,<NUM>/mol, at least <NUM>,<NUM>/mol, at least <NUM>,<NUM>/mol, at least <NUM>,<NUM>/mol, or at least <NUM>,<NUM>/mol. In some embodiments, the PAS polymer has an Mw of no more than <NUM>,<NUM>/mol, no more than <NUM>,<NUM>/mol, no more than <NUM>,<NUM>/mol, no more than <NUM>,<NUM>/mol, or no more than <NUM>,<NUM>/mol. In some embodiments, the PAS polymer has an Mw of from <NUM>,<NUM>/mol to <NUM>,<NUM>/mol, from <NUM>,<NUM>/mol to <NUM>,<NUM>/mol, from <NUM>,<NUM>/mol to <NUM>,<NUM>/mol, from <NUM>,<NUM>/mol to <NUM>,<NUM>/mol, or from <NUM>,<NUM>/mol to <NUM>,<NUM>/mol. Mw can be measured as described in the Examples below.

The PAS polymer can be amorphous or semi-crystalline. As used herein, an amorphous polymer has an enthalpy of fusion ("ΔHf") of no more than <NUM> Joules/g ("J/g"). The person of ordinary skill in the art will recognize that when the PAS is amorphous, it lacks a detectable Tm. Accordingly, where a PAS polymer has a Tm, the person of ordinary skill in the art will recognize that it refers to semi-crystalline polymer. Preferably, the PAS polymer is semi-crystalline. In some embodiments, the PAS polymer has a ΔHf of at least <NUM> J/g, at least <NUM> J/g, at least, or at least <NUM> J/g. In some embodiments, the PAS polymer has a ΔHf of no more than <NUM> J/g, no more than <NUM> J/g or no more than <NUM> J/g. In some embodiments, the PAS polymer has a ΔHf of from <NUM> J/g to <NUM> J/g or from <NUM> J/g to <NUM> J/g. ΔHf can be measured as described in the Examples below.

In some embodiments, the PAS polymer has a Tg of at least <NUM> or at least <NUM>. In some embodiments, the PAS polymer has a Tg of no more than <NUM> or no more than <NUM>. In some embodiments, the PAS polymer has a Tg of from <NUM>° C to <NUM>, from <NUM>° C to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In some embodiments, the PAS polymer has a melting temperature ("Tm") of at least <NUM>, at least <NUM>, at least <NUM>, or at least <NUM>. In some embodiments, the PAS polymer has a Tm of no more <NUM>, no more than <NUM>, no more than <NUM>, or no more than <NUM>. In some embodiments, the PAS polymer has a Tm of from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In some embodiments, the PAS polymer has a crystallization temperature ("Tc") of at least <NUM> or at least <NUM>. In some embodiments, the PAS polymer has a Tc of no more than <NUM>, or no more than <NUM>. In some embodiments, the PAS polymer has a Tc of from <NUM> to <NUM> or from <NUM> to <NUM>. Tg, Tm and Tc can be measured as described in the Examples below. In some embodiments, the PAS polymer (PASP) is amorphous and it has a Tg of at least <NUM>, at least <NUM>, or at least <NUM>.

In some embodiments, the PAS polymer (PASP) has an impact strength of at least <NUM> Joules per gram ("J/g"), or at least <NUM> J/g. In some embodiments, the PAS polymer (PASP) has an impact strength of no more than <NUM> J/g or no more than <NUM> J/g. In some embodiments, the PAS polymer has an impact strength of from <NUM> J/g to <NUM> J/g, from <NUM> J/g to <NUM> J/g, from <NUM> J/g to <NUM> J/g, from <NUM> J/g to <NUM> J/g. Unless explicitly stated otherwise, as used herein, impact strength refers to notched-Izod impact strength, measured as described in the Examples below.

In some embodiments, the PAS polymer (PASP) has an elastic modulus of at least <NUM> GPa, at least <NUM> GPa, or at least <NUM> GPa. Elastic modulus can be measured as described in the Examples, below.

The PAS polymer (PASP) can be synthesized by methods known in the art. In one approach, the PAS polymer synthesis includes a polymerization process and a subsequent recovery process. The polymerization process includes a polymerization reaction, in which at least a dihaloaromatic monomer, a dihalofluorene monomer (distinct from the first dihaloaromatic monomer) and a sulfur compound are polymerized in a solvent to form the PAS polymer, and a termination, in which the polymerization reaction is stopped.

The polymerization reaction involves reacting in a reaction mixture a dihaloaromatic compound having the following formula: X<NUM>-Ar<NUM>-X<NUM>; a dihalofluorene monomer having the following formula: X<NUM>-Ar<NUM>-X<NUM>; and a sulfur compound (collectively, "reaction components") in a polymerization solvent according to the following scheme:
<CHM>
where X<NUM> to X<NUM> are independently selected halogens, -Ar<NUM>- and -Ar<NUM>- are as given above, and SC is a sulfur compound described below. Preferably, X<NUM> and X<NUM> are the same halogen and X<NUM> and X<NUM> are the same halogen. More preferably, X<NUM> and X<NUM> are both chlorine or X<NUM> and X<NUM> are both bromine. In some embodiments, X<NUM> and X<NUM> are both chlorine and X<NUM> and X<NUM> are both bromine. Preferably, X<NUM>-Ar<NUM>-X<NUM> is a para-dihalobenzene, most preferably para-dichlorobenzene. The person of ordinary skill in the art will recognize that -Ar<NUM>- and -Ar<NUM>- in reaction scheme (S1) are incorporated into recurring units (RPAS1) and (RPAS2), respectively, as described in detail above and shown in reaction scheme (S1). Accordingly, the preferences and embodiments for -Ar<NUM>- and -Ar<NUM>- described above for recurring units (RPAS1) and (RPAS2) are also applicable for -Ar<NUM>- and -Ar<NUM>- in reaction scheme (S1). For example, in some embodiments, X<NUM>-Ar<NUM>-X<NUM> is a dihalofluorene monomer selected from the group consisting of <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dimethyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dipropyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dihexyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-dioctyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-didodecyl-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-di-(<NUM>-ethylhexyl)-<NUM>H-fluorene; <NUM>,<NUM>-dibromo-<NUM>,<NUM>-diphenyl-<NUM>H-fluorene; and <NUM>,<NUM>-dibromo-<NUM>,<NUM>-difluoro-<NUM>H-fluorene. In some embodiments, the reaction components can further include a molecular weight modifying agent.

The sulfur compound (SC) is selected from the group consisting of thiosulfates, thioureas, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and bisulfides, and hydrogen sulfide. Preferably, the sulfur compound is an alkali metal sulfide. In some embodiments, the alkali metal sulfide is generated in situ from an alkali metal hydrosulfide and an alkali metal hydroxide. For example, Na<NUM>S is a particularly desirable alkali metal sulfide. Na<NUM>S can be generated in situ from NaSH and NaOH.

The polymerization solvent is selected such that it is a solvent for reaction components at the reaction temperature (discussed below). In some embodiments, the polymerization solvent is a polar aprotic solvent. Examples of desirable polar aprotic solvents include, but are not limited to, hexamethylphosphoramide, tetramethylurea, n,n-ethylenedipyrrolidone, N-methyl-<NUM>-pyrrolidone ("NMP"), pyrrolidone, caprolactam, n-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, and <NUM>,<NUM>-dimethyl-<NUM>-imidazolidinone. Preferably, the polymerization solvent is NMP. In embodiments, in which the polymerization solvent includes NMP, NMP can react with NaOH to form N-methyl-<NUM>,<NUM>-aminobutanoate ("SMAB").

As noted above, in some embodiments, the reaction components further include a molecular weight modifying agent. The molecular weight modifying agent increases the molecular weight of the PAS polymer, relative to a synthesis scheme not including the molecular weight modifying agent. Preferably, the molecular weight modifying agent is an alkali metal carboxylate. Alkali metal carboxylates are represented by the formula: R'CO<NUM>M', where R' is selected from the group consisting of a C<NUM> to C<NUM> hydrocarbyl group, a C<NUM> to C<NUM> hydrocarbyl group and a C<NUM> to C<NUM> hydrocarbyl group; and M' is selected from the group consisting of lithium, sodium, potassium, rubidium or cesium. Preferably M' is sodium or potassium, most preferably sodium. Preferably, the alkali metal carboxylate is sodium acetate.

The polymerization reaction is performed by contacting the reaction components at a reaction temperature selected such that X<NUM>-Ar<NUM>-X<NUM>, X<NUM>-Ar<NUM>-X<NUM> and SC polymerize to form the PAS polymer. In some embodiments, the reaction temperature is from <NUM> to <NUM>, or from <NUM> to <NUM>. The reaction time (time duration of the polymerization reaction) can be from <NUM> minutes to <NUM> days or from <NUM> hour to <NUM> hours. During the polymerization reaction, the pressure (reaction pressure) is selected to maintain the reaction components in the liquid phase. In some embodiments, the reaction pressure can be from <NUM> kPa at the gauge (<NUM> pounds per square inch gauge ("psig")) to <NUM> kPa at the gauge (<NUM> psig), from <NUM> kPa at the gauge (<NUM> psig) to <NUM> kPa at the gauge (<NUM> psig), or from <NUM> kPa at the gauge (<NUM> psig) to <NUM> kPa at the gauge (<NUM> psig).

The polymerization reaction can be terminated by cooling the reaction mixture to a temperature at which the polymerization reaction ceases. "Reaction mixture" refers to the mixture formed during the polymerization reaction and contains any remaining reaction components, formed PAS polymer and reaction by-products. The cooling can be performed using a variety of techniques known in the art. In some embodiments, the cooling can be done by flashing rapidly the reaction mixture. In some embodiments, the cooling can include liquid quenching. In liquid quenching, a quench liquid is added to the reaction mixture to cool the reaction mixture. In some embodiments, the quench liquid is selected from the group consisting of the polymerization solvent, water and a combination thereof. In some embodiments, the temperature of the quench liquid can be from about <NUM> to <NUM>. In some embodiments, the temperature of the quench liquid can be from <NUM> to <NUM> (e.g. in embodiments in which the quench liquid is the solvent) or from <NUM> to <NUM> (e.g. in embodiments in which the quench liquid is water). The cooling can be further facilitated by use of a reactor jacket or coil, to cool the reaction vessel in which the polymerization reaction is performed ("polymerization reactor"). For clarity, termination of the polymerization reaction does not imply that complete reaction of the reaction components. Generally, termination is initiated at a time when the polymerization reaction is substantially complete or reaches the targeted yield or when further reaction of the reaction components would not result in a significant increase in average molecular weight of the PAS polymer.

After termination, the PAS polymer is present as a PAS polymer mixture. The PAS polymer mixture includes water, the polymerization solvent, reaction by-products including salts (e.g. sodium chloride and sodium acetate); PAS oligomers, and any unreacted reaction components (collectively, "post-reaction compounds"). Generally, after termination, the PAS polymer mixture is present as a slurry, having a liquid phase and a solid phase containing the PAS polymer (precipitates from the solvent during liquid quenching or during the flashing). In some embodiments, the PAS polymer mixture can be present as wet PAS polymer, for example, by filtration of the slurry after termination. PAS polymer synthesis, including polymerization and termination, and recovery, including water treatment, acid treatment and metal cation treatment, is discussed in <CIT> ("the '<NUM> patent") and incorporated by reference herein in its entirety.

Subsequent to termination, a recovery process is implemented. The recovery process includes one or more washes, where each wash includes contacting the PAS polymer formed during polymerization with a liquid. The liquid of each wash is independently selected from water, aqueous acid, and an aqueous metal cation solution. Examples of post-reaction recovery processes are discussed in the '<NUM> patent. Based upon the disclosure herein, the person of ordinary skill in the art will know how to select a recovery process to obtain the PAS polymer described herein.

Subsequent to the recovery process, the PAS polymer mixture can be dried. The drying can be performed at any temperature which can substantially dry the PAS polymer mixture, to yield a dried PAS polymer. Desirably, the drying process is selected to help prevent oxidative curing of the PAS polymer. For example, if the drying process is conducted at a temperature of at least <NUM>, the drying can be conducted in a substantially non-oxidizing atmosphere (e.g., in a substantially oxygen free atmosphere or at a pressure less than atmospheric pressure, for example, under vacuum). When the drying process is conducted at a temperature less than <NUM>, the drying process can be facilitated by performing the drying at a pressure less than atmospheric pressure so the liquid component can be vaporized from the PAS polymer mixture. When the drying is performed at a temperature of less than <NUM>, the presence of a gaseous oxidizing atmosphere (e.g. air) generally does not result in a detectable curing of the PAS polymer.

The polymer composition (PC) includes the PAS polymer and at least one other component selected from the group consisting of selected from the group consisting of reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants (including, but not limited to, halogen free flame retardants), nucleating agents and antioxidants.

In some embodiments, the concentration of the PAS polymer in the polymer composition (PC) is at least <NUM> wt. %, at least <NUM> wt. %, at least <NUM> wt. % by weight, at least <NUM> wt. % or at least <NUM> wt. In some embodiments, the concentration of the PAS polymer in the polymer composition (PC) is no more than <NUM> wt. %, no more than <NUM> wt. %, no more than <NUM> wt. %, no more than <NUM> wt. %, no more than <NUM> wt. %, no more than <NUM> wt. %, no more than <NUM> wt. % or no more than <NUM> wt. In some embodiments, the concentration of the PAS polymer in the polymer composition (PC) is from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt%, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, or from <NUM> wt. % to <NUM> wt. As used herein, the concentration of a component in the polymer composition is relative to the total weight of the polymer composition (PC), unless explicitly stated otherwise.

In some embodiments, the polymer composition (PC) further includes a reinforcing agent (also called reinforcing fibers or fillers). They can be selected from fibrous and particulate reinforcing agents. A fibrous reinforcing filler is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least <NUM>, at least <NUM>, at least <NUM> or at least <NUM>. In some embodiments, the reinforcing fibers (e.g. glass fibers or carbon fibers) have an average length of from <NUM> to <NUM>. In some such embodiments, the reinforcing fibers have an average length of from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In alternative embodiments, the reinforcing fibers have an average length of from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM> or from <NUM> to <NUM>. The average length of the reinforcing fibers can be taken as the average length of the reinforcing fibers prior to incorporation into the polymer composition (PC) or can be taken as the average length of the reinforcing fiber in the polymer composition (PC).

The reinforcing filler may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers and wollastonite. In the case of glass fibers, they can be round (circular cross section) or flat (non-circular cross-section including, but not limited to, oval, elliptical or rectangular).

Among fibrous fillers, glass fibers are preferred; they include chopped strand A-, E-, C-, D-, S- and R-glass fibers, as described in <NPL>. Preferably, the filler is chosen from fibrous fillers. It is more preferably a reinforcing fiber that is able to withstand the high temperature applications.

In some embodiments, the concentration of the reinforcing agent (e.g. glass or carbon fibers) in the polymer composition (PC) is at least <NUM> wt. %, at least <NUM> wt. %, at least <NUM> wt. % or at least <NUM> wt. In some embodiments, the concentration of the reinforcing agent in the polymer composition (PC) is no more <NUM> wt. %, no more than <NUM> wt. % or no more than <NUM> wt. In some embodiments, the concentration of the reinforcing agent in the polymer composition (PC) is from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, or from <NUM> wt. % to <NUM> wt.

In some embodiments, the polymer composition (PC) further includes a flame retardant. The flame retardant can be a halogen-free flame retardant or a halogenated flame retardant. Preferably, the flame retardant is a halogen-free flame retardant. Halogen-free flame retardants include, but are not limited to, organophosphorous compounds selected from the group consisting of phosphinic salts ("phosphinates"), diphosphinic salts ("diphosphinates") and condensation products thereof. Phosphinates are preferred organophosphorous compound. Suitable phosphinates include, but are not limited to, those described in <CIT> and incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinates, calcium phosphinates, and zinc phosphinates. Among aluminum phosphinates, aluminium ethylmethylphosphinate and aluminium diethylphosphinate and combinations thereof are preferred. Halogenated flame retardants include, but are not limited to, <NUM>,<NUM>-bis(tribromophenoxy)ethane, brominated epoxy oligomers, brominated polystyrene, chlorendic anhydride, chlorinated paraffins, decabromobiphenyl, decabromodiphenylethane, decabromodiphenyloxide, dechlorane plus, dibromoneopentylglycol, ethylene-bis(<NUM>,<NUM>-dibromonorbornane-<NUM>,30dicarboximide), ethylene-bis(tetrabromophthalimide), halogenated polyetherpolyols, hexabromocyclododecane, octabromodiphenyloxide, octabromotrimethylphenylindane, pentabromodiphenyloxide, poly(dibromostyrene), poly(pentabromobenzylacrylate), tetrabromo-bisphenol-A, tetrabromo-bisphenol-A, bis(<NUM>,<NUM>-dibromopropyl ether), tetrabromophthalate diols and tetrabromophthalic anhydride. Preferably, the halogenated flame retardant is a brominated or chlorinated compound or polymer.

In some embodiments, the concentration of the flame retardant in the polymer composition (PC) is at least <NUM> wt. %, at least <NUM> wt. %, or at least <NUM> wt. In some embodiments, the concentration of the flame retardant in the polymer composition (PC) is no more than <NUM> wt. %, no more than <NUM> wt. %, or no more than <NUM> wt. In some embodiments, the concentration of the flame retardant in the polymer composition (PC) is from <NUM> wt. % to <NUM> wt. %, from <NUM> wt. % to <NUM> wt. %, or from <NUM> wt. % to <NUM> wt.

The polymer composition (PC) may also include a toughener. A toughener is generally a low Tg polymer, with a Tg for example below room temperature, below <NUM> or even below -<NUM>° C. As a result of its low Tg, the toughener are typically elastomeric at room temperature. Tougheners can be functionalized polymer backbones.

The polymer backbone of the toughener can be selected from elastomeric backbones comprising polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene-rubbers (EPR); ethylene-propylene-diene monomer rubbers (EPDM); ethylene-acrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA), ethylene-vinylacetate (EVA); acrylonitrile-butadiene-styrene rubbers (ABS), block copolymers styrene ethylene butadiene styrene (SEBS); block copolymers styrene butadiene styrene (SBS); core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or mixture of one or more of the above.

When the toughener is functionalized, the functionalization of the backbone can result from the copolymerization of monomers which include the functionalization or from the grafting of the polymer backbone with a further component.

Specific examples of functionalized tougheners are notably terpolymers of ethylene, acrylic ester and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate; copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styrene-acrylonitrile copolymers grafted with maleic anhydride; ABS copolymers grafted with maleic anhydride. Further specific examples of functionalized tougheners also include copolymers of ethylene and glycidyl methacrylate as well as copolymers of ethylene and methacrylic acid.

The toughener may be present in the composition (C) in a total amount of greater than <NUM> wt. %, greater than <NUM> wt. % or greater than <NUM> wt. %, based on the total weight of the composition (C). The toughener may be present in the composition (C) in a total amount of less than <NUM> wt. %, less than <NUM> wt. %, less than <NUM> wt. % or less than <NUM> wt. %, based on the total weight of the polymer composition (PC).

The composition (C) may also comprise other conventional additives commonly used in the art, including plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.

In some embodiments, the polymer composition (PC) consists essentially of the PAS polymer (PASP) and a glass fiber. In some embodiments, the polymer composition (PC) consists essentially of the PAS polymer (PASP) and a toughener. In some embodiments, the polymer composition (PC) consists essentially of the PAS polymer (PASP), glass fiber and a toughener. As used herein with respect to the polymer composition (PC), consists essentially of indicates that the concentration of components other than the explicitly recited components is less than <NUM> wt. %, less than <NUM> wt. %, less than <NUM> wt. %, less than <NUM> wt. %, less than <NUM> wt. %, less than <NUM> wt. %, or less than <NUM> wt.

The polymer composition (PC) may also comprise one or more additional polymers, preferably additional PAS polymers (PASP). For example, in some embodiments, the polymer composition (PC) can include a plurality of PAS polymers (PASP), each distinct from each other and each comprising recurring units (RPAS1), (RPAS2), or a combination thereof.

In some embodiments, the polymer composition (PC) includes the PAS polymer (PASP) and from <NUM> wt. % to <NUM> wt. % of a glass fiber (it may, of course, including other components such as a toughener). In some such embodiments, the concentration of the PAS polymer (PASP) in the polymer composition (PC) is from <NUM> wt. % to <NUM> wt. In some embodiments, the polymer composition (PC) includes the PAS polymer (PASP) and from <NUM> wt. % to <NUM> wt. % of a toughener. In some such embodiments, the concentration of the PAS polymer (PASP) in the polymer composition (PC) is from <NUM> wt. % to <NUM> wt.

The polymer compositions (PC) can be made using methods well known in the art. In one approached, the polymer compositions (PC) can be made by melt-blending the PAS polymer and the specific components (e.g. a reinforcing filler, a flame retardant, a stabilizer, and of any other components).

Any melt-blending method may be used for mixing polymeric ingredients and non-polymeric ingredients in the context of the present invention. For example, polymeric ingredients and non-polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches. When the polymeric ingredient and non-polymeric ingredient are gradually added in batches, a part of the polymeric ingredients and/or non-polymeric ingredients is first added, and then is melt-mixed with the remaining polymeric ingredients and non-polymeric ingredients that are subsequently added, until an adequately mixed composition is obtained. If a reinforcing agent presents a long physical shape (for example, a long glass fiber), drawing extrusion molding may be used to prepare a reinforced composition.

The PAS polymer and polymer composition (PC) can be desirably incorporated into articles.

The article can notably be used in mobile electronics, LED packaging, oil and gas components, food contact components (including, but not limited to, food film and casing), electrical and electronic components (including, but not limited to, power unit components for computing, data-system and office equipment and surface mounted technology compatible connectors and contacts), medical device components, construction components (including, but not limited to, pipes, connectors, manifolds and valves, for cooling and heating systems; boiler and meter components; gas systems pipes and fittings; and electrical protection devices for mini-circuit breakers, contactors, switches and sockets), industrial components, plumbing components (including, but not limited to, pipes, valves, fittings, manifolds, shower taps and shower valves), automotive components, and aerospace components (including, but not limited to, interior cabin components).

The article can be, for example, a mobile electronic device component. As used herein, a "mobile electronic device" refers to an electronic device that is intended to be conveniently transported and used in various locations. A mobile electronic device can include, but is not limited to, a mobile phone, a personal digital assistant ("PDA"), a laptop computer, a tablet computer, a wearable computing device (e.g., a smart watch, smart glasses and the like), a camera, a portable audio player, a portable radio, global position system receivers, and portable game consoles. The mobile electronic device component may include, for example, a radio antenna and the composition (C). In this case, the radio antenna can be a WiFi antenna or an RFID antenna. The mobile electronic device component may also be an antenna housing.

In some embodiments, the mobile electronic device component is an antenna housing. In some such embodiments, at least a portion of the radio antenna is disposed on the polymer composition (PC). Additionally or alternatively, at least a portion of the radio antenna can be displaced from the polymer composition (PC). In some embodiments, the device component can be of a mounting component with mounting holes or other fastening device, including but not limited to, a snap fit connector between itself and another component of the mobile electronic device, including but not limited to, a circuit board, a microphone, a speaker, a display, a battery, a cover, a housing, an electrical or electronic connector, a hinge, a radio antenna, a switch, or a switchpad. In some embodiments, the mobile electronic device can be at least a portion of an input device.

Examples of electric and electronics devices include, but are not limited to, connectors, contactors, switches, and flexible and non-flexible printed circuit boards.

Examples of oil and gas components include, but are not limited to, compressor rings, poppets, back-up seal rings, electrical connectors, labyrinth seals, motor end plates, bearings, bushings, suck rod guides and down hole tubing.

Examples of automotive components include, but are not limited to, components in thermal management systems (including, but not limited to, thermostat housings, water inlet/outlet valves, water pumps, water pump impellers, and heater cores and end caps), air management system components (including, but not limited to, turbocharger actuators, turbocharger by-pass valves, turbocharger hoses, EGR valves, CAC housings, exhaust gas recirculation systems, electronic controlled throttle valves, and hot air ducts), transmission components and launch device components (including, but not limited to, dual clutch transmissions, automated manual transmissions, continuously variable transmissions, automatic transmissions, torque convertors, dual mass flywheels, power takeoffs, clutch cylinders, seal rings, thrust washers, thrust bearings, needle bearings, and check balls), automotive electronic components, automotive lighting components (including, but not limited to, motor end caps, sensors, ECU housings, bobbins and solenoids, connectors, circuit protection/relays, actuator housings, Li-Ion battery systems, and fuse boxes), traction motor and power electronic components (including, but not limited to, battery packs), fuel and selective catalytic reduction ("SCR") systems (including, but not limited to, SCR module housings and connectors, SCR module housings and connectors, fuel flanges, rollover valves, quick connects, filter housings, fuel rails, fuel delivery modules, fuel hoses, fuel pumps, fuel injector o-rings, and fuel hoses), fluid system components (e.g. fuels system components) (including, but not limited to inlet and outlet valves and fluid pump components), interior components (e.g. dashboard components, display components, and seating components), and structural and lightweighting components (e.g. gears and bearings, sunroofs, brackets and mounts, electrical battery housings, thermal management components, braking system elements, and pump and EGR systems).

The article can be molded from the PAS polymer (PASP) or polymer composition (PC) by any process adapted to thermoplastics, e.g. extrusion, injection molding, blow molding, rotomolding or compression molding.

The article can be printed from the PAS polymer (PASP) or polymer composition (PC) by a process comprising a step of extrusion of the material, which is for example in the form of a filament, or comprising a step of laser sintering of the material, which is in this case in the form of a powder.

In some embodiments, the PAS polymer (PASP) or polymer composition (PC) can be desirably incorporated into three dimensional printing applications. One application is direct to a method for manufacturing a three-dimensional ("3D") object with an additive manufacturing system, comprising providing a part material comprising the PAS polymer (PASP) or polymer composition (PC) of the present invention, and printing layers of the three-dimensional object from the part material.

The PAS polymer (PASP) or polymer composition (PC) can therefore be in the form of a thread or a filament to be used in a process of 3D printing, e.g. Fused Filament Fabrication, also known as Fused Deposition Modelling ("FDM").

The PAS polymer (PASP) or polymer composition (PC) can also be in the form of a powder, for example a substantially spherical powder, to be used in a process of 3D printing, e.g. Selective Laser Sintering (SLS).

The PAS polymer (PASP) or polymer composition (PC) can be incorporated into a composite. A composite includes continuous reinforcing fibers imbedded in a thermoplastic matrix. In some embodiments, the continuous reinforcing fiber is selected from glass fiber, carbon fibers, aluminum fiber, titanium fiber, magnesium fiber, boron carbide fibers, rock wool fiber, steel fiber, aramid fiber, natural fiber (e.g. cotton, linen and wood) and any combination of one or more, thereof. Preferably, the continuous reinforcing fiber is glass fiber or carbon fiber. As used herein, continuous reinforcing fibers are reinforcing fibers that have an average length in the longest dimension of at least <NUM> millimeters ("mm"), at least <NUM>, at least <NUM> or at least <NUM>. The thermoplastic matrix includes the PAS polymer (PASP) or polymer composition (PC). The composite can be a unidirectional composite (e.g. a tape) or a multidirectional composite (e.g. a woven fabric, a mat, or a layered fabric).

The present invention relates to the use of the PAS polymers (PASP) and polymer compositions (PC) or articles for manufacturing the articles as described above. The present invention also relates to the use of the above-described PAS polymers (PASP) or polymer compositions (C) for 3D printing an object.

The present examples demonstrate the synthesis and the thermal and impact performance of the PAS polymers described herein.

Example <NUM>: (<NUM> mol% DBDMF co-PPS) A <NUM>-L autoclave reactor was charged with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBDMF (<NUM> mol), and <NUM> NMP. The reactor was purged and pressurized to <NUM> kPa at the gauge (<NUM> psig) with nitrogen and set to stir continuously at <NUM> rpm. A separate addition vessel was charged with <NUM> DCB (<NUM> mol) and <NUM> NMP. The addition vessel was purged and pressurized to <NUM> kPa at the gauge (<NUM> psig) with nitrogen, and heated to <NUM>. The reactor was heated to <NUM> at <NUM>/min. Upon reaching <NUM>, the reactor was vented through a condenser and ~<NUM> of a clear condensate was collected under a small stream of nitrogen (<NUM>/min) until the reactor reached <NUM>. At this point, the condenser was removed, the nitrogen flow was stopped, and the DCB/NMP mixture in the addition vessel was added to the reactor. The addition vessel was charged with an additional <NUM> NMP, purged and pressurized to <NUM> kPa at the gauge (<NUM> psig) with nitrogen, and the contents were immediately added to the reactor. The sealed reactor was held at <NUM> for <NUM> hours, heated to <NUM> at <NUM>/min, held at <NUM> for <NUM> hours, cooled to <NUM> at <NUM>/min, and finally allowed to cool to room temperature. The resulting slurry was diluted with <NUM> NMP, removed from the reactor, heated to <NUM>, and filtered through a medium porosity sintered glass filter. The filter cake was washed once with <NUM> warm NMP (<NUM>). The solids were stirred for <NUM> minutes in <NUM> heated DI water (<NUM>) and subjected to filtration on a medium porosity glass filter, a process that was repeated five times in total. The rinsed solids were dried in a vacuum oven overnight at <NUM> under nitrogen to give <NUM> of a white granular solid. GPC, DSC, the Young's elastic modulus (measured with ASTM Type V specimens), and ASTM Notched Izod data for this and following examples are given in the Table below.

Example <NUM>: (<NUM> mol% DBDMF co-PPS) Synthesized according to procedure from Example <NUM> with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBDMF (<NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. Afforded <NUM> of a white granular solid.

Counter Example <NUM>: (PPS homopolymer) Synthesized according to procedure from Example <NUM> (except that no DBDMF was used) with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. Afforded <NUM> of a granular white solid.

Counter Example <NUM>: (<NUM> mol% DBBP co-PPS) Synthesized according to procedure from Example <NUM> (except that DBBP was used instead of DBDMF) with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBBP (<NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. Afforded <NUM> of a granular white solid.

Counter Example <NUM>: (<NUM> mol% DBBP co-PPS) Synthesized according to procedure from Counter Example <NUM> with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBBP (<NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. Afforded <NUM> of a granular white solid.

Counter Example <NUM>: (<NUM> mol% DBBP co-PPS) Synthesized according to procedure from Counter Example <NUM> with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBBP (<NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. Afforded <NUM> of a granular off-white solid.

Counter Example <NUM>: (<NUM> mol% DBBP co-PPS) Synthesized according to procedure from Counter Example <NUM> with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBBP (<NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. Afforded <NUM> of a granular light yellow solid.

Counter Example <NUM>: (<NUM> mol% DBF co-PPS) Synthesized according to procedure from Example <NUM> (except that DBF was used instead of DBDMF) with <NUM> sodium hydroxide (<NUM> mol), <NUM> sodium acetate (<NUM> mol), <NUM> NaSH (<NUM> wt%, <NUM> mol), <NUM> DBF (<NUM> mol), <NUM> DCB (<NUM> mol), and <NUM> total NMP. The polymerization resulted in higher than usual maximum pressure (<NUM> kPa at the gauge [<NUM> psig] vs. <NUM> kPa at the gauge [a typical <NUM> psig]). The reaction mixture was a brown sludge that smelled strongly of thiophenol and other decomposition species. A portion was rinsed according to procedure to afford a light brown powder with low molecular weight that was not suitable for injection molding.

Thermal Performance: Tg, Tm, Tc, and ΔHf were determined using differential scanning calorimetry ("DSC"), according to ASTM D3418 employing a heating and cooling rate of <NUM>/min. Three scans were used for each DSC test: a first heat up to <NUM>, followed by a first cool down to <NUM>, followed by a second heat up to <NUM>. Tc was determined from the first cool. Tg, Tm, and ΔHf were determined from the second heat.

Molecular Weight: Mw was determined by gel permeation chromatography (GPC) at <NUM> using a PL <NUM> high temperature GPC with a <NUM>-chloronaphtalene mobile phase with polystyrene standards.

Impact Performance: Notched Izod values were determined according to ASTM D256 using <NUM> (<NUM> inch) flex bars at room temperature.

Modulus: The Young's elastic modulus was determined according to ASTM D638 using Type V tensile bars at room temperature with a testing speed of <NUM> per minute (<NUM> inches per minute).

Testing results are displayed in Table <NUM>. In Table <NUM>, "E" denotes an Example and "CE" denotes a counter example.

Referring to Table <NUM>, comparison of E3 with CE7, demonstrates that, surprisingly, high Mw PAS polymer incorporating a dihalofluorene cannot be synthesized when R<NUM> and R<NUM> (in X<NUM>-Ar<NUM>-X<NUM>, above) are both hydrogen. CE7, including recurring units from a dihalofluorene where R<NUM> and R<NUM> are hydrogen, had a Mw of only <NUM>,<NUM>/mol (Tg could not be determined due to low molecular weight). Notably, the impact performance and modulus of CE7 could not be measured, as the samples were too brittle to make a notch. Surprisingly, under the same conditions and when R<NUM> and R<NUM> were replaced with methyl groups (E3), PAS polymer having a Mw of <NUM>,<NUM>/mol was obtained.

Comparison of E1 to E3 with CE1 to CE5 demonstrates that, surprisingly, PAS polymers incorporating the dihalofluorene monomers described herein have both increased Tg and impact strength, relative to analogous PAS homopolymers and PAS polymers incorporating DBBP. For example, comparison of E1 to E3 to CE1 demonstrates that, relative to a PPS homopolymer, the PAS polymer incorporating recurring units formed from DBDMF had increased Tg and impact strength, at relative low concentrations of DBDMF. Similarly results were observed when comparing E1 to E3 with CE2 to CE4, respectively. Furthermore, comparison of E1 to E3 to with CE1 to CE4 demonstrates that the PAS polymers incorporating recurring units formed from DBDMF still has excellent elastic modulus.

Claim 1:
A poly(arylene sulfide) ("PAS") polymer (PASP) comprising recurring units RPAS1 and RPAS2, represented by the following formulae, respectively:

        [-Ar<NUM>-S-],     (<NUM>)

        [-Ar<NUM>-S-],     (<NUM>)

wherein
- -Ar<NUM>- is selected from the group of formulae consisting of:
<CHM>
<CHM>
<CHM>
- -Ar<NUM>- is represented by the following formula:
<CHM>
- R and R', at each instance, is independently selected from the group consisting of a C<NUM>-C<NUM> alkyl group, a C<NUM>-C<NUM> alkylaryl group, a C<NUM>-C<NUM> aralkyl group, a C<NUM>-C<NUM> arylene group, and a C<NUM>-C<NUM> aryloxy group;
- T is selected from the group consisting of a bond, -CO-, -SO<NUM>-, -O-, -C(CH<NUM>)<NUM>, phenyl and -CH<NUM>-;
- i, at each instance, is an independently selected integer from <NUM> to <NUM>;
- j and k, at each instance, are an independently selected integer from <NUM> to <NUM>;
- R<NUM> is selected from the group consisting of a hydrogen, a fluorine, a C<NUM>-C<NUM> alkyl group, a C<NUM>-C<NUM> alkyaryl group, and a C<NUM>-C<NUM> aryl group; and
- R<NUM> is selected from the group consisting of a fluorine, a C<NUM>-C<NUM> alkyl group, a C<NUM>-C<NUM> alkyaryl group, and a C<NUM>-C<NUM> aryl group.