Poly(arylene sulfide) polymers and corresponding polymer compositions and articles

Abstract

Described herein are poly(arylene sulfide) ("PAS") polymers (PASPs) containing repeat units formed from selected dihalofluorene monomers. Surprisingly, at relatively low concentrations of dihalofluorene monomers, the PAS polymers (PASPs) exhibit significantly increased glass transition temperatures ("T") relative to similar PAS homopolymers and PAS polymers (PASPs) containing repeat units formed from 4,4'-dibromobiphenyl ("DBBP"). g ") and impact performance. At the same time, PAS polymers (PASP) also retain a high modulus. Furthermore, PAS polymers (PASP) do not contain repeating units formed from polyhalogenated biphenyls (e.g., DBBP and polychlorinated biphenyls) and are therefore not currently subject to restrictive government regulations. The excellent thermal properties (T g , T c and T m Due to their thermal conductivity and impact resistance, PAS polymers (PASPs) and PAS polymer compositions may be desirably incorporated into a variety of articles, including, but not limited to, automotive articles, electrical and electronic articles, aerospace articles, and oil and gas articles.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 915150, filed October 15, 2019, and European Patent Application No. 19206822.9, filed November 4, 2019, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to poly(arylene sulfide) ("PAS") polymers that have excellent thermal and mechanical properties. The present invention also relates to PAS polymer compositions, methods for making PAS polymers and PAS compositions, and articles incorporating PAS polymers and PAS polymer compositions. [Background technology]

[0003] Poly(arylene sulfide) ("PAS") polymers generally have high chemical resistance and desirable mechanical properties, but they also have relatively low T g (typically 85°C to 98°C), which limits their use in some applications (e.g., thermoplastic composites), as well as low toughness (impact strength).

[0004] PAS polymer T gKnown methods for increasing the toughness and modulus of a PAS polymer involve forming a polymer composition containing an additive (e.g., a toughening agent) and incorporating a hard comonomer, such as 4,4'-dibromobiphenyl ("DBBP"), into the PAS polymer. While toughening agents increase the toughness of PAS polymers, they also dramatically reduce the modulus of elasticity (e.g., typically less than 2.5 GPa). For DBBP, relatively high concentrations are required to achieve a Tg above 100°C, but the melting temperature in such cases is also very high (above 360°C), making processing extremely difficult. Furthermore, DBBP is a polybrominated biphenyl ("PBB"), which belongs to a class of highly regulated compounds (polyhalogenated biphenyls). For example, DBBP is regulated by the U.S. Environmental Protection Agency under the Toxic Substances Control Act ("TSCA"). Therefore, the use of DBBP monomers is nearly impossible under current regulatory regulations. Summary of the Invention

[0005] In a first aspect, the present invention provides a polymerizable composition comprising repeating units R each represented by the formula: PAS1 and R PAS2 and a poly(arylene sulfide) (“PAS”) polymer (PASP) comprising: [-Ar1-S-] (1) [-Ar2-S-] (2) (In the formula, - -Ar1- is [ka] is selected from the group of formulas consisting of - -Ar2- is a compound of the following formula [ka] is represented by R and R' are, in each case, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups and C6-C18 independently selected from the group consisting of aryloxy groups; - T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl, and -CH2-; - i, in each occurrence, is an independently selected integer from 0 to 4; j and k, in each occurrence, are independently selected integers from 0 to 3; - R1 is hydrogen, fluorine, C1-C 12 Alkyl groups, C7-C 24 Alkylaryl groups and C6-C 24 aryl groups; and - R2 is fluorine, C1-C 12 Alkyl groups, C7-C 24 Alkylaryl groups and C6-C 24 aryl groups).

[0006] In some embodiments, -Ar2- is selected from the group consisting of the dihalofluorene monomer diradicals 2,7-dibromo-9,9-dimethyl-9H-fluorene; 2,7-dibromo-9,9-dipropyl-9H-fluorene; 2,7-dibromo-9,9-dihexyl-9H-fluorene; 2,7-dibromo-9,9-dioctyl-9H-fluorene; 2,7-dibromo-9,9-didodecyl-9H-fluorene; 2,7-dibromo-9,9-di-(2-ethylhexyl)-9H-fluorene; 2,7-dibromo-9,9-diphenyl-9H-fluorene; and 2,7-dibromo-9,9-difluoro-9H-fluorene.

[0007] In some embodiments, the PAS polymer (PASP) has a T g Additionally or alternatively, in some embodiments, the PAS polymer (PASP) has a T m In yet further or alternative embodiments, the PAS polymer (PASP) has an impact strength of at least 30 J / g as determined according to ASTM D256.

[0008] In another aspect, the present invention relates to a polymer composition (PC) comprising a PAS polymer (PASP) and a reinforcing agent, glass fiber, or both.

[0009] In a further aspect, the present invention relates to an automotive component, an oil and gas component, or an aerospace component comprising a PAS polymer (PASP) or a polymer composition (PC).

[0010] In another aspect, the present invention relates to a method for making a PAS polymer (PASP), comprising reacting in a reaction mixture a dihaloaromatic compound having the formula: X1-Ar1-X2; a dihalofluorene monomer having the formula: X3-Ar2-X4; and a sulfur compound, wherein X1-X4 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 disulfides, and hydrogen sulfide; preferably, the sulfur compound is an alkali metal sulfide; and most preferably, the sulfur compound is Na2S. DETAILED DESCRIPTION OF THE INVENTION

[0011] Described herein are poly(arylene sulfide) ("PAS") polymers (PASPs) containing repeat units formed from selected dihalofluorene monomers. Surprisingly, at relatively low concentrations of dihalofluorene monomers, the PAS polymers (PASPs) exhibit significantly increased glass transition temperatures ("T") relative to similar PAS homopolymers and PAS polymers (PASPs) containing repeat units formed from 4,4'-dibromobiphenyl ("DBBP"). g") and impact performance. At the same time, PAS polymers (PASP) also retain a high modulus of elasticity (also referred to herein as elastic modulus or Young's modulus). Furthermore, PAS polymers (PASP) do not contain repeating units formed from polyhalogenated biphenyls (e.g., DBBP and polychlorinated biphenyls) and, therefore, are not currently subject to restrictive government regulations. The excellent thermal properties (T g , T c and T m Due to their thermal conductivity and impact resistance, PAS polymers (PASPs) and PAS polymer compositions may be desirably incorporated into a variety of articles, including, but not limited to, automotive articles, electrical and electronic articles, aerospace articles, and oil and gas articles.

[0012] As used herein, "free of" a given repeat unit means that the concentration of the given repeat unit in the PAS polymer (PASP) is less than 1 mol %, preferably less than 0.5 mol %, more preferably less than 0.1 mol %, even more preferably less than 0.01 mol %, even more preferably less than 0.001 mol %, and most preferably 0 mol % (undetectable).

[0013] In this application, any description, even if made in connection with a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Furthermore, when an element or component is referred to as being included in and / or selected from a list of recited elements or components, in the relevant embodiments expressly contemplated herein, the element or component can be any one of the individually recited elements or components, or can be selected from a group consisting of any two or more of the explicitly recited elements or components; it should be understood that any element or component recited in a list of elements or components can also be omitted from such a 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 ranges and equivalents.

[0014] Unless otherwise specifically limited, the terms "alkyl," and 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, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl. Unless otherwise specifically stated, each alkyl and aryl group may be unsubstituted or substituted with halogen, amino, hydroxy, sulfo, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C6 alkyl, or aryl. 15 Aryloxy or C6-C 15 and aryl, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are met. The term "halogen" or "halo" includes fluorine, chlorine, bromine, and iodine.

[0015] The term "aryl" refers to a phenyl, indanyl, or naphthyl group. An aryl group can contain one or more alkyl groups, in which case it is sometimes referred to as an "alkylaryl," and can be composed, for example, of an aromatic group and two C1-C6 groups (e.g., methyl or ethyl). An aryl group can also contain one or more heteroatoms, such as N, O, or S, in which case it is sometimes referred to as a "heteroaryl" group, and these heteroaromatic rings can be fused with 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. An aryl or heteroaryl substituent can be unsubstituted or can be selected from the group consisting of halogen, hydroxy, C1-C6 alkoxy, sulfo, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C6 alkyl, and the like. 15 Aryloxy or C6-C 15It may be substituted with one or more substituents selected from, but not limited to, aryl, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied.

[0016] PAS polymer (PASP) PAS polymer (PASP) is a polymer consisting of repeating units (R PAS1 ) and repeating units (R PAS2 ): [-Ar1-S-] and (1) [-Ar2-S-] (2) Including, -Ar1- is formed from a dihaloaromatic monomer (as described below) and is of the following group of formulas: [ka] (wherein R is, in each case, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups and C6-C 18 aryloxy groups; T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl, and -CH2-; i, in each occurrence, is an independently selected integer from 0 to 4; and j, in each occurrence, is an independently selected integer from 0 to 3. For clarity, each benzyl ring in the above formula has 4-i hydrogens (formulas (3) and (4)) or 3-j hydrogens (formula (5)). Thus, when i or j is zero, the corresponding benzyl ring is unsubstituted. Similar notation is used throughout this specification. Furthermore, each formula (3) to (5) contains two dashed bonds, one of which is connected to a repeating unit (R PAS1 ) to the distinct sulfur atom, and the other bond is to the repeating unit (R PAS1 ) to an atom outside the repeat unit (e.g., an adjacent repeat unit). Similar notation is used throughout.

[0017] In a preferred embodiment, i and j are zero in each instance. Preferably, -Ar1- is represented by either formula (3) or (4), more preferably formula (3) ([-Ar1-S-] corresponding to the repeating unit of polyphenylene sulfide), and even more preferably -Ar1- is represented by the following formula: [ka] Most preferably, -Ar1- is represented by formula (6), where i is zero.

[0018] -Ar2- is formed from a dihalofluorene monomer (as described below) and has the formula: [ka] (wherein R' is, in each case, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups and C6-C 18 aryloxy groups; k, at each occurrence, is an independently selected integer from 0 to 3; R1 is hydrogen, fluorine, C1-C 12 Alkyl groups, C7-C 24 Alkylaryl groups and C6-C 24 aryl groups; and R2 is selected from the group consisting of fluorine, C1-C 12 Alkyl groups, C7-C 24 Alkylaryl groups and C6-C 24 aryl groups). Preferably, R1 and R2 are both fluorine, or neither R1 nor R2 is fluorine. Preferably, neither R1 nor R2 is fluorine.

[0019] As demonstrated in the examples below, when R1 and R2 are both hydrogen, high molecular weight PAS polymers cannot be formed. In some embodiments, R1 and R2 are C1-C12 Alkyl groups, C7-C 24 Alkylaryl groups and C6-C 24 In some such embodiments, R1 is independently selected from the group consisting of C1-C aryl groups. 12 is an alkyl group or R2 is C1-C 12 alkyl group; more preferably, both R1 and R2 are C1-C 12 most preferably, R1 and R2 are —CH3 groups. In some embodiments, R1 is hydrogen and R2 is a C1-C 12 Alkyl groups, C7-C 24 Alkylaryl groups and C6-C 24 In some such embodiments, R2 is selected from the group consisting of C1-C aryl groups. 12 It is an alkyl group, preferably a -CH3 group.

[0020] In some embodiments, -Ar2- is of the formula: [ka] In some such embodiments, k is zero at each position. Additionally or alternatively, in some embodiments, R1 is C1 to C 12 is an alkyl group, and R2 is a C1-C 12 alkyl group, or both R1 and R2 are C1-C 12Preferably, R1 is -CH3 and R2 is -CH3, or both R1 and R2 are -CH3. In some embodiments, -Ar2- is a diradical of a dihalofluorene monomer selected from the group consisting of 2,7-dibromo-9,9-dimethyl-9H-fluorene; 2,7-dibromo-9,9-dipropyl-9H-fluorene; 2,7-dibromo-9,9-dihexyl-9H-fluorene; 2,7-dibromo-9,9-dioctyl-9H-fluorene; 2,7-dibromo-9,9-didodecyl-9H-fluorene; 2,7-dibromo-9,9-di-(2-ethylhexyl)-9H-fluorene; 2,7-dibromo-9,9-diphenyl-9H-fluorene; and 2,7-dibromo-9,9-difluoro-9H-fluorene. For clarity, the dihalofluorene monomer diradical refers to the diradical formed from the dehalogenation of the specified halogen of the dihalofluorene monomer (X3 and X4 in the following reaction diagram (S1)). For example, the diradical of the dihalofluorene monomer 2,7-dibromo-9,9-dimethyl-9H-fluorene refers to the diradical formed from the debromination of 2,7-dibromo-9,9-dimethyl-9H-fluorene. In some embodiments, -Ar1- is represented by formula (6), where i is equal to zero, and -Ar2- is the diradical of a dihalofluorene monomer selected from the aforementioned group of dihalofluorene monomers. In one such embodiment, -Ar2- is the diradical of 2,7-dibromo-9,9-dimethyl-9H-fluorene.

[0021] In another embodiment, -Ar1- is represented by a formula selected from the group consisting of Formulas (3)-(5), and -Ar2- is a diradical of spirobifluorene. In some such embodiments, the spirobifluorene is 2,7-dihalo-9,9-spirobifluorene or 2,2,7,7-tetrahalo-9,9-spirobifluorene, preferably 2,7-dibromo-9,9-spirobifluorene or 2,2,7,7-tetrabromo-9,9-spirobifluorene. In one such embodiment, -Ar1- is represented by Formula (6), and i is zero.

[0022] In some embodiments, the repeating units (R PAS1 ) and (R PAS2 ) is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol%. As used herein, the molar concentration of a repeat unit in a polymer is relative to the total number of repeat units in that polymer, unless expressly specified otherwise. In some embodiments, the molar concentration of a repeat unit (R PAS1 ) is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 85 mol%, at least 88 mol%, at least 90 mol%, at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 98.5 mol%, or at least 99 mol%.

[0023] As mentioned above, the repeating unit (R PAS2 At relatively low concentrations of ), PAS polymers (PASP) exhibit significantly increased T while maintaining or improving toughness. g In some embodiments, the repeating unit (R PAS2 ) is at least 0.5 mol %, at least 1 mol %, at least 1.5 mol %, at least 2 mol %, or at least 2.5 mol %. In some embodiments, the concentration of repeating units (R PAS2 ) is 15 mol % or less, 12 mol % or less, 10 mol % or less, or 8 mol % or less. PAS2 The number of moles of the repeating unit (R ) is 0.5 mol % to 15 mol %, 0.5 mol % to 12 mol %, 0.5 mol % to 10 mol %, 0.5 mol % to 8 mol %, 1 mol % to 15 mol %, 1 mol % to 12 mol %, 1 mol % to 10 mol %, 1 mol % to 8 mol %, 2 mol % to 8 mol %, or 2.5 mol % to 8 mol %. In some embodiments, the number of moles of the repeating unit (R PAS1 ) and (R PAS2 The number of repeating units (R PAS2) is at least 1 mol %, at least 1.5 mol %, at least 2 mol %, or at least 2.5 mol %. In some embodiments, the ratio of the number of repeating units (R PAS1 ) and (R PAS2 The number of repeating units (R PAS2 In some embodiments, the ratio of the number of repeating units (R PAS1 ) and (R PAS2 The number of repeating units (R PAS2 ) is 1 mol % to 15 mol %, 1 mol % to 12 mol %, 1 mol % to 10 mol %, 1 mol % to 8 mol %, 2 mol % to 8 mol %, or 2.5 mol % to 8 mol %. Nevertheless, in some embodiments, the PAS polymer (PASP) may have a higher concentration of repeat units (R PAS2 In some such embodiments, the repeating unit (R PAS2 The concentration of ) is 0.5 mol % to 99 mol % or less, 80 mol % or less, 70 mol % or less, 60 mol % or less, 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less.

[0024] Of course, in some embodiments, the PAS polymers are each different from one another and have repeating units (R PAS1 ) and (R PAS2 In one such embodiment, the PAS polymer comprises one or more additional repeat units according to formula (1) or one or more additional repeat units according to formula (2). In some embodiments that include additional repeat units according to formulas (1) and (2), the total concentration of repeat units according to formulas (1) and (2) is determined by the repeat unit (R PAS1 ) and (R PAS2 ) is within the ranges given above for the repeat units (R PAS1 ) and (R PAS2Of course, in other embodiments, the concentration of the additional repeat units according to formulas (1) and (2), and the number of additional repeat units according to formula (1) relative to the total number of repeat units according to formulas (1) and (2), may vary depending on the repeat units (R PAS1 ) and (R PAS2 ) is different from the range shown above.

[0025] In some embodiments, the PAS polymer has a weight average molecular weight ("M") of at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, at least 30,000 g / mol, or at least 35,000 g / mol. w In some embodiments, the PAS polymer has an M of 150,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, 85,000 g / mol or less, or 80,000 g / mol or less. w In some embodiments, the PAS polymer has an M of 10,000 g / mol to 150,000 g / mol, 20,000 g / mol to 100,000 g / mol, 25,000 g / mol to 90,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 35,000 g / mol to 80,000 g / mol. w M w can be measured as described in the Examples below.

[0026] PAS polymers may be amorphous or semi-crystalline. As used herein, amorphous polymers have an enthalpy of fusion ("ΔH") of 5 Joules / g ("J / g") or less. f Those skilled in the art will appreciate that if a PAS is amorphous, it will have a detectable T m It will be recognized that a PAS polymer does not have a Tm. Thus, one of ordinary skill in the art will recognize that when a PAS polymer has a Tm, it is referred to as a semi-crystalline polymer. Preferably, the PAS polymer is semi-crystalline. In some embodiments, the PAS polymer has a ΔH of at least 10 J / g, at least 20 J / g, at least, or at least 25 J / g. fIn some embodiments, the PAS polymer has a ΔH of 90 J / g or less, 70 J / g or less, or 60 J / g or less. f In some embodiments, the PAS polymer has a ΔH of 10 J / g to 90 J / g or 20 J / g to 70 J / g. f ΔH f can be measured as described in the Examples below.

[0027] In some embodiments, the PAS polymer has a T g In some embodiments, the PAS polymer has a T of 200° C. or less, or 150° C. or less. g In some embodiments, the PAS polymer has a T of 95°C to 200°C, 99°C to 150°C, 95°C to 200°C, or 99°C to 150°C. g In some embodiments, the PAS polymer has a melting temperature ("T") of at least 200°C, at least 220°C, at least 240°C, or at least 250°C. m In some embodiments, the PAS polymer has a T of 350° C. or less, 320° C. or less, 300° C. or less, or 285° C. or less. m In some embodiments, the PAS polymer has a T of 200°C to 350°C, 220°C to 320°C, 240°C to 300°C, or 250°C to 285°C. m In some embodiments, the PAS polymer has a crystallization temperature ("T") of at least 140°C or at least 150°C. c In some embodiments, the PAS polymer has a T c In some embodiments, the PAS polymer has a T of 140°C to 250°C or 150°C to 220°C. c T g , T m and Tc can be measured as described in the Examples below. In some embodiments, the PAS polymer (PASP) is amorphous and has a Tg of at least 90°C, at least 95°C, or at least 100°C.

[0028] In some embodiments, the PAS polymer (PASP) has an impact strength of at least 30 Joules per gram ("J / g"), or at least 35 J / g. In some embodiments, the PAS polymer (PASP) has an impact strength of 150 J / g or less, or 125 J / g or less. In some embodiments, the PAS polymer has an impact strength of 30 J / g to 150 J / g, 35 J / g to 150 J / g, 30 J / g to 125 J / g, or 35 J / g to 125 J / g. Unless otherwise specified, impact strength as used herein refers to notched Izod impact strength, measured as described in the Examples below.

[0029] In some embodiments, the PAS polymer (PASP) has a modulus of at least 3 GPa, at least 3.1 GPa, or at least 3.2 GPa. The modulus can be measured as described in the Examples below.

[0030] Synthesis of PAS polymer PAS polymers (PASPs) can be synthesized by methods known in the art. In one approach, the synthesis of PAS polymers involves a polymerization process followed by a recovery process. The polymerization process includes a polymerization reaction in which at least a dihaloaromatic monomer, a dihalofluorene monomer (different from the first dihaloaromatic monomer), and a sulfur compound are polymerized in a solvent to form a PAS polymer, and a termination reaction to terminate the polymerization reaction.

[0031] The polymerization reaction involves reacting in a reaction mixture a dihaloaromatic compound having the formula: X1-Ar1-X2, a dihalofluorene monomer having the formula: X3-Ar2-X4, and a sulfur compound (collectively "reactants") in a polymerization solvent according to the following scheme: [ka] (wherein X1-X4 are independently selected halogens, -Ar1- and -Ar2- are as defined above, and SC is a sulfur compound as described below). Preferably, X1 and X2 are the same halogen, and X3 and X4 are the same halogen. More preferably, X1 and X2 are both chlorine, or X3 and X4 are both bromine. In some embodiments, X1 and X2 are both chlorine, and X3 and X4 are both bromine. Preferably, X1-Ar1-X2 is para-dihalobenzene, most preferably para-dichlorobenzene. Those skilled in the art will recognize that -Ar1- and -Ar2- in Reaction Scheme (S1) correspond to the repeating units (R PAS1 ) and (R PAS2 ) and thus, PAS1 ) and (R PAS2 The preferences and embodiments of -Ar1- and -Ar2- described above for (S1) can also be applied to -Ar1- and -Ar2- in Reaction Scheme (S1). For example, in some embodiments, X3-Ar2-X4 is a dihalofluorene monomer selected from the group consisting of 2,7-dibromo-9,9-dimethyl-9H-fluorene; 2,7-dibromo-9,9-dipropyl-9H-fluorene; 2,7-dibromo-9,9-dihexyl-9H-fluorene; 2,7-dibromo-9,9-dioctyl-9H-fluorene; 2,7-dibromo-9,9-didodecyl-9H-fluorene; 2,7-dibromo-9,9-di-(2-ethylhexyl)-9H-fluorene; 2,7-dibromo-9,9-diphenyl-9H-fluorene; and 2,7-dibromo-9,9-difluoro-9H-fluorene. In some embodiments, the reaction components can further include a molecular weight modifier.

[0032] 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 disulfides, 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, NaS is a particularly desirable alkali metal sulfide. NaS can be generated in situ from NaSH and NaOH.

[0033] The polymerization solvent is selected to be a solvent for the reactants at the reaction temperature (described 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-2-pyrrolidone ("NMP"), pyrrolidone, caprolactam, n-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. Preferably, the polymerization solvent is NMP. In embodiments where the polymerization solvent comprises NMP, NMP can be reacted with NaOH to form N-methyl-1,4-aminobutanoate ("SMAB").

[0034] As noted above, in some embodiments, the reaction components further comprise a molecular weight modifier. The molecular weight modifier increases the molecular weight of the PAS polymer compared to a synthesis scheme that does not include a molecular weight modifier. Preferably, the molecular weight modifier is an alkali metal carboxylate. Alkali metal carboxylates have the formula: R'CO2M', where R' is a C1-C 20 Hydrocarbyl groups, C1-C 20and C1-C5 hydrocarbyl groups, and M' is selected from the group consisting of lithium, sodium, potassium, rubidium, or cesium. Preferably, M' is sodium or potassium, and most preferably sodium. Preferably, the alkali metal carboxylate is sodium acetate.

[0035] The polymerization reaction is carried out by contacting the reactants at a reaction temperature selected so that X1-Ar1-X2, X3-Ar2-X4, and SC polymerize to form a PAS polymer. In some embodiments, the reaction temperature is 170°C to 450°C, or 200°C to 285°C. The reaction time (duration of the polymerization reaction) can be 10 minutes to 3 days, or 1 hour to 8 hours. The pressure (reaction pressure) is selected to maintain the reactants in the liquid phase during the polymerization reaction. In some embodiments, the reaction pressure can be 0 pounds per square inch gauge ("psig") to 400 psig, 30 psig to 300 psig, or 100 psig to 250 psig.

[0036] 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, including any remaining reaction components, the PAS polymer formed, and reaction by-products. Cooling can be accomplished using a variety of techniques known in the art. In some embodiments, cooling can be accomplished by rapidly flashing the reaction mixture. In some embodiments, cooling can include a liquid quench. In a liquid quench, a quenching liquid is added to the reaction mixture to cool the reaction mixture. In some embodiments, the quenching liquid is selected from the group consisting of the polymerization solvent, water, and combinations thereof. In some embodiments, the temperature of the quenching liquid can be from about 15°C to 99°C. In some embodiments, the temperature of the quenching liquid can be from 54°C to 100°C (e.g., in embodiments where the quenching liquid is a solvent) or from 15°C to 32°C (e.g., in embodiments where the quenching liquid is water). Cooling can be further facilitated by cooling the reaction vessel in which the polymerization reaction occurs (the "polymerization reactor") using a reactor jacket or coils. For clarity, termination of the polymerization reaction does not imply complete reaction of the reactants. Generally, termination is initiated when the polymerization reaction is substantially complete or reaches a target yield, or when further reaction of the reactants does not result in a significant increase in the average molecular weight of the PAS polymer.

[0037] After termination, the PAS polymer exists as a PAS polymer mixture. The PAS polymer mixture includes water, polymerization solvent, reaction by-products such as salts (e.g., sodium chloride and sodium acetate), PAS oligomers, and any unreacted reaction components (collectively, the "post-reaction compound"). Typically, after termination, the PAS polymer mixture exists as a slurry (precipitated from the solvent during liquid quenching or flashing) having a liquid phase containing the PAS polymer and a solid phase. In some embodiments, the PAS polymer mixture can exist as a wet PAS polymer, for example, by filtering the slurry after termination. PAS polymer synthesis, including polymerization and termination, and recovery, including water treatment, acid treatment, and metal cation treatment, are described in U.S. Patent Application Publication No. 2015 / 0175748 to Fodor et al., filed December 19, 2013 (the "'748 patent"), which is incorporated herein by reference in its entirety.

[0038] Following termination, a recovery process is carried out. The recovery process includes one or more washes, each involving contacting the PAS polymer formed during polymerization with a liquid. Each wash liquid is independently selected from water, an aqueous acid solution, and an aqueous metal cation solution. Examples of post-reaction recovery processes are described in the '748 patent. Based on the disclosure herein, one skilled in the art will know how to select a recovery process to obtain the PAS polymers described herein.

[0039] Following the recovery process, the PAS polymer mixture can be dried. Drying can be carried out at any temperature that allows the PAS polymer mixture to be substantially dry to obtain 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 carried out at a temperature of at least 100°C, drying can be carried out in a substantially non-oxidizing atmosphere (e.g., a substantially oxygen-free atmosphere or at a pressure below atmospheric pressure, e.g., under vacuum). If the drying process is carried out at a temperature below 100°C, the drying process can be accelerated by carrying out the drying at a pressure below atmospheric pressure, thereby allowing liquid components to evaporate from the PAS polymer mixture. If drying is carried out at a temperature below 100°C, the presence of a gaseous oxidizing atmosphere (e.g., air) generally does not result in detectable curing of the PAS polymer.

[0040] PAS polymer composition The polymer composition (PC) comprises a PAS polymer and at least one other component selected from the group consisting of reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants (such as, but not limited to, halogen-free flame retardants), nucleating agents, and antioxidants.

[0041] In some embodiments, the concentration of the PAS polymer in the polymer composition (PC) is at least 20 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, or at least 45 wt%. In some embodiments, the concentration of the PAS polymer in the polymer composition (PC) is 99.95 wt% or less, 99 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 70 wt% or less, or 60 wt% or less. In some embodiments, the concentration of the PAS polymer in the polymer composition (PC) is 20 wt% to 99.95 wt%, 20 wt% to 95 wt%, 20 wt% to 85 wt%, 20 wt% to 80 wt%, 20 wt% to 70 wt%, or 20 wt% to 60 wt%. As used herein, concentrations of components in the polymer composition are based on the total weight of the polymer composition (PC) unless otherwise specified.

[0042] In some embodiments, the polymer composition (PC) further comprises a reinforcing agent (also referred to as a reinforcing fiber or filler). These can be selected from fibrous reinforcing agents and particulate reinforcing agents. A fibrous reinforcing filler is herein considered to be a material having a length, width, and thickness in which the average length is significantly greater than both the width and the thickness. Generally, such materials have an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness, of at least 5, at least 10, at least 20, or at least 50. In some embodiments, the reinforcing fibers (e.g., glass fibers or carbon fibers) have an average length of 3 mm to 50 mm. In some such embodiments, the reinforcing fibers have an average length of 3 mm to 10 mm, 3 mm to 8 mm, 3 mm to 6 mm, or 3 mm to 5 mm. In alternative embodiments, the reinforcing fibers have an average length of 10 mm to 50 mm, 10 mm to 45 mm, 10 mm to 35 mm, 10 mm to 30 mm, 10 mm to 25 mm, or 15 mm to 25 mm. The average length of the reinforcing fibers can be understood as the average length of the reinforcing fibers before they are incorporated into the polymer composition (PC), or as the average length of the reinforcing fibers in the polymer composition (PC).

[0043] The reinforcing fillers may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, etc.), glass fibers, carbon fibers, synthetic polymer 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 may be round (circular cross-section) or flat (non-circular cross-section, such as, but not limited to, oval, elliptical, or rectangular).

[0044] Among fibrous fillers, glass fibers are preferred; these include chopped strand A-, E-, C-, D-, S-, and R-glass fibers as described in Additives for Plastics Handbook, 2nd edition, John Murphy, Chapter 5.2.3, pp. 43-48. Preferably, the filler is selected from fibrous fillers. More preferably, the filler is a reinforcing fiber capable of withstanding high temperature applications.

[0045] In some embodiments, the concentration of reinforcing agent (e.g., glass or carbon fiber) in the polymer composition (PC) is at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt%. In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is 70 wt% or less, 65 wt% or less, or 60 wt% or less. In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is 5 wt% to 70 wt%, 10 wt% to 70 wt%, 10 wt% to 65 wt%, 10 wt% to 60 wt%, 15 wt% to 60 wt%, or 20 wt% to 60 wt%.

[0046] In some embodiments, the polymer composition (PC) further comprises a flame retardant. The flame retardant may 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, organophosphorus compounds selected from the group consisting of phosphinates ("phosphinates"), diphosphinates ("diphosphinates"), and condensation products thereof. Phosphinates are preferred organophosphorus compounds. Suitable phosphinates include, but are not limited to, those described in U.S. Patent No. 6,365,071 to Jenewein et al., issued April 2, 2002, which is incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinate, calcium phosphinate, and zinc phosphinate. Among aluminum phosphinates, aluminum ethyl methyl phosphinate and aluminum diethyl phosphinate, and combinations thereof, are preferred. Halogenated flame retardants include, but are not limited to, 1,2-bis(tribromophenoxy)ethane, brominated epoxy oligomers, brominated polystyrene, chlorendic anhydride, chlorinated paraffins, decabromobiphenyl, decabromodiphenylethane, decabromodiphenyl oxide, Dechlorane Plus, dibromoneopentyl glycol, ethylene-bis(5,6-dibromonorbornane-2,30dicarboximide), ethylene-bis(tetrabromophthalimide), halogenated polyether polyols, hexabromocyclododecane, octabromodiphenyl oxide, octabromotrimethylphenylindane, pentabromodiphenyl oxide, poly(dibromostyrene), poly(pentabromobenzyl acrylate), tetrabromo-bisphenol-A, tetrabromo-bisphenol-A, bis(2,3-dibromopropyl ether), tetrabromophthalate diol, and tetrabromophthalic anhydride. Preferably, the halogenated flame retardant is a brominated or chlorinated compound or polymer.

[0047] In some embodiments, the concentration of the flame retardant in the polymer composition (PC) is at least 1 wt%, at least 3 wt%, or at least 5 wt%. In some embodiments, the concentration of the flame retardant in the polymer composition (PC) is 30 wt% or less, 25 wt% or less, or 20 wt% or less. In some embodiments, the concentration of the flame retardant in the polymer composition (PC) is 1 wt% to 30 wt%, 3 wt% to 25 wt%, or 5 wt% to 20 wt%.

[0048] The polymer composition (PC) may also contain a toughening agent. The toughening agent generally has a low T g and the T g Its low T g As a result, the toughening agent is typically elastomeric at room temperature. The toughening agent can be a functionalized polymer backbone.

[0049] The polymer backbone of the toughening agent may be selected from elastomeric backbones comprising polyethylene and copolymers thereof, such as ethylene-butene; ethylene-octene; polypropylene and copolymers thereof; polybutene; polyisoprene; ethylene-propylene-rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS); block copolymer styrene ethylene butadiene styrene (SEBS); block copolymer styrene butadiene styrene (SBS); core-shell elastomers of the methacrylate-butadiene-styrene (MBS) type, or mixtures of one or more of the above.

[0050] If the toughening agent is functionalized, backbone functionalization can occur by copolymerization of monomers containing the functionalization or by grafting the polymer backbone with additional components.

[0051] Specific examples of functionalized toughening agents include, among others, terpolymers of ethylene, acrylic esters, 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, and ABS copolymers grafted with maleic anhydride. Further specific examples of functionalized toughening agents include copolymers of ethylene and glycidyl methacrylate, and copolymers of ethylene and methacrylic acid.

[0052] The toughening agents may be present in composition (C) in a total amount of more than 1 wt%, more than 2 wt%, or more than 3 wt%, based on the total weight of composition (C). The toughening agents may be present in composition (C) in a total amount of less than 30 wt%, less than 20 wt%, less than 15 wt%, or less than 10 wt%, based on the total weight of polymer composition (PC).

[0053] Composition (C) may also contain other conventional additives commonly used in the art, such as 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), heat stabilizers, light stabilizers, flame retardants, nucleating agents, and antioxidants.

[0054] In some embodiments, the polymer composition (PC) consists essentially of a PAS polymer (PASP) and glass fibers. In some embodiments, the polymer composition (PC) consists essentially of a PAS polymer (PASP) and a reinforcing agent. In some embodiments, the polymer composition (PC) consists essentially of a PAS polymer (PASP), glass fibers, and a reinforcing agent. As used herein with respect to a polymer composition (PC), "consisting essentially of" indicates that the concentration of components other than those explicitly listed is less than 5 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, less than 0.05 wt%, or less than 0.01 wt%.

[0055] The polymer composition (PC) may also include one or more additional polymers, preferably additional PAS polymers (PASPs). For example, in some embodiments, the polymer composition (PC) may include a plurality of repeating units (R PAS1 ), (R PAS2 ), or a combination thereof.

[0056] In some embodiments, the polymer composition (PC) comprises a PAS polymer (PASP) and 10% to 60% by weight of glass fiber (which may, of course, include other components such as a toughening agent). In some such embodiments, the concentration of the PAS polymer (PASP) in the polymer composition (PC) is 20% to 90% by weight. In some embodiments, the polymer composition (PC) comprises a PAS polymer (PASP) and 5% to 30% by weight of a toughening agent. In some such embodiments, the concentration of the PAS polymer (PASP) in the polymer composition (PC) is 70% to 95% by weight.

[0057] Preparation of polymer composition (PC) The polymer composition (PC) can be made using methods well known in the art. In one approach, the polymer composition (PC) can be made by melt blending the PAS polymer with certain ingredients (e.g., reinforcing fillers, flame retardants, stabilizers, and other optional ingredients).

[0058] Any melt-blending method can be used to mix the polymeric and non-polymeric components involved in the present invention. For example, the polymeric and non-polymeric components can be fed into a melt mixer, such as a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, or a Banbury mixer, and the addition step can be simultaneous addition of all components or batchwise addition. When the polymeric and non-polymeric components are added gradually in a batchwise manner, a portion of the polymeric and / or non-polymeric components is added first and then melt-mixed with the remaining polymeric and non-polymeric components added thereafter until a well-mixed composition is obtained. When the reinforcing agent has a long physical shape (e.g., long glass fibers), stretch extrusion can be used to prepare the reinforced composition.

[0059] Articles and uses The PAS polymers and polymer compositions (PC) can be desirably incorporated into articles.

[0060] The articles can be used in portable electronics, LED packaging, oil and gas components, food contact components (including, but not limited to, food films and casings), electrical and electronic components (including, but not limited to, components of power supplies for computers, data systems and office equipment, and connectors and contacts compatible with surface mount technology), medical equipment components, building components (including, but not limited to, pipes, connectors, manifolds, and valves for cooling and heating systems; boiler and meter components; gas system pipes and fittings; and electrical protection devices, contactors, switches, and sockets for mini-circuit breakers), 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, onboard cabin components), among others.

[0061] The article may be, for example, a portable electronic device component. As used herein, "portable electronic device" refers to an electronic device intended to be conveniently carried and used in various locations. Portable electronic devices may include, but are not limited to, mobile phones, personal digital assistants ("PDAs"), laptop computers, tablet computers, wearable computing devices (e.g., smart watches, smart glasses, etc.), cameras, portable audio players, portable radios, global positioning system receivers, and portable game consoles. The portable electronic device component may include, for example, a wireless antenna and the composition (C). In this case, the wireless antenna may be a WiFi antenna or an RFID antenna. The portable electronic device component may also be an antenna housing.

[0062] In some embodiments, the portable electronic device component is an antenna housing. In some such embodiments, at least a portion of the wireless antenna is disposed on the polymer composition (PC). Additionally or alternatively, at least a portion of the wireless antenna can be detachable from the polymer composition (PC). In some embodiments, the device component can be an attachment component having mounting holes or other fastening devices (including, but not limited to, a snap-fit ​​connector between itself and another component of the portable 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 wireless antenna, a switch, or a switch pad). In some embodiments, the portable electronic device can be at least a portion of an input device.

[0063] Examples of electrical and electronic devices include, but are not limited to, connectors, contactors, switches, flexible and non-flexible printed circuit boards.

[0064] Examples of oil and gas components include, but are not limited to, compressor rings, poppets, backup seal rings, electrical connectors, labyrinth seals, motor end plates, bearings, bushings, suck rod guides, and downhole tubing.

[0065] Examples of automotive components include 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 bypass valves, turbocharger hoses, EGR valves, CAC housings, exhaust gas recirculation systems, electronically controlled throttle valves, and hot air ducts), transmission and launch device components (including, but not limited to, dual clutch transmissions, automated manual transmissions, continuously variable transmissions, automatic transmissions, torque converters, dual mass flywheels, power take-offs, clutch cylinders, seal rings, thrust washers, thrust bearings, needle bearings, and check balls), automotive electronics, 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 motors and power electronics (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., fuel 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 lightweight components (e.g., gears and bearings, sunroofs, brackets and mounts, electrical battery housings, thermal management components, brake system elements, and pumps and EGR systems).

[0066] Articles can be molded from the PAS polymer (PASP) or polymer composition (PC) by any process compatible with thermoplastics, such as extrusion, injection molding, blow molding, rotational molding, or compression molding.

[0067] Articles can be printed from PAS polymers (PASP) or polymer compositions (PC) by a process that includes a step of extrusion of the material, for example in the form of a filament, or by a process that includes a step of laser sintering of the material, in which case the material is in powder form.

[0068] In some embodiments, the PAS polymer (PASP) or polymer composition (PC) may be desirably incorporated into three-dimensional printing applications. One application relates to a method for producing 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.

[0069] Thus, the PAS polymer (PASP) or polymer composition (PC) can be in the form of a yarn or filament used in the process of 3D printing, for example, fused filament manufacturing (also known as fused deposition modeling "FDM").

[0070] The PAS polymer (PASP) or polymer composition (PC) may be in the form of a powder, for example a substantially spherical powder, for use in 3D printing, for example in the process of selective laser sintering (SLS).

[0071] The PAS polymer (PASP) or polymer composition (PC) can be incorporated into a composite material. The composite material includes continuous reinforcing fibers embedded in a thermoplastic matrix. In some embodiments, the continuous reinforcing fibers are selected from glass fibers, carbon fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, aramid fibers, natural fibers (e.g., cotton, linen, and wood), and any combination of one or more thereof. Preferably, the continuous reinforcing fibers are glass fibers or carbon fibers. As used herein, continuous reinforcing fibers are reinforcing fibers having an average length in their longest dimension of at least 5 millimeters ("mm"), at least 10 mm, at least 25 mm, or at least 50 mm. The thermoplastic matrix includes the PAS polymer (PASP) or polymer composition (PC). The composite material can be a unidirectional composite (e.g., a tape) or a multidirectional composite (e.g., a woven fabric, mat, or layered fabric).

[0072] The present invention also relates to the use of the PAS polymer (PASP) and polymer composition (PC) or article described above for manufacturing the article. The present invention also relates to the use of the PAS polymer (PASP) or polymer composition (C) described above for 3D printing an object. [Example]

[0073] This example demonstrates the synthesis and thermal and impact performance of the PAS polymers described herein.

[0074] raw materials 1-Methyl-2-pyrrolidone ("NMP") (>99.0%): Obtained from TCI Sodium hydrogen sulfide ("NaSH") (55-60% by weight): available from AkzoNobel 1,4-Dichlorobenzene ("DCB") (≥99): Obtained from Alfa Aesar Sodium hydroxide (≥97.0%): obtained from Fisher Chemical Sodium acetate (≥99%): obtained from VWR Chemicals 2,7-Dibromofluorene ("DBF") (≥97%): obtained from AccelaChemBio 2,7-Dibromo-9,9-dimethylfluorene (“DBDMF”) (≥97%): obtained from AccelaChemBio 2,7-Dibromo-9,9-dihexylfluorene ("DBDHF") (≥98%): obtained from Alfa Aesar 4,4'-Dibromobiphenyl ("DBBP"): obtained from Matrix Scientific

[0075] Synthesis of PAS polymer Example 1: (2.5 mol% DBDMF co-PPS) A 1 L autoclave reactor was charged with 32.31 g sodium hydroxide (0.808 mol), 21.44 g sodium acetate (0.261 mol), 77.57 g NaSH (57.24 wt%, 0.792 mol), 6.97 g DBDMF (0.020 mol), and 214 mL NMP. The reactor was purged, pressurized to 10 psig with nitrogen, and set for continuous stirring at 400 rpm. A separate addition vessel was charged with 113.51 g DCB (0.772 mol) and 50 g NMP. The addition vessel was purged, pressurized to 90 psig with nitrogen, and heated to 100°C. The reactor was heated to 240°C at 1.5°C / min. After reaching 150°C, the reactor was condensed, and approximately 40 mL of clear condensate was collected under a small nitrogen flow (60 mL / min) until the reactor reached 200°C. 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 30 mL of NMP, purged, and pressurized to 90 psig with nitrogen, and the contents were immediately added to the reactor. The sealed reactor was held at 240°C for 2 hours, heated to 265°C at 1.5°C / min, held at 265°C for 2 hours, cooled to 200°C at 1.0°C / min, and finally allowed to cool to room temperature. The resulting slurry was diluted with 200 mL of NMP, removed from the reactor, heated to 80°C, and filtered through a medium-porosity sintered glass filter. The filter cake was washed once with 100 mL of warm NMP (60°C). The solid was stirred in 300 mL of heated DI water (70° C.) for 15 minutes and filtered through a medium porosity glass filter; this process was repeated a total of five times. The rinsed solid was dried in a vacuum oven under nitrogen at 100° C. overnight to yield 80.21 g of a white granular solid. GPC, DSC, Young's modulus (measured using ASTM Type V specimens), and ASTM notched Izod data for this and subsequent examples are shown in the table below.

[0076] Example 2: (5 mol% DBDMF co-PPS) Synthesized according to the procedure of Example 1 using 31.88 g sodium hydroxide (0.797 mol), 21.16 g sodium acetate (0.258 mol), 74.00 g NaSH (59.21 wt%, 0.782 mol), 13.76 g DBDMF (0.039 mol), 109.14 g DCB (0.742 mol), and a total of 291 mL NMP. 82.73 g of a white granular solid was obtained.

[0077] Example 3: (10 mol% DBDMF co-PPS) Synthesized according to the procedure of Example 1 using 32.80 g sodium hydroxide (0.820 mol), 21.77 g sodium acetate (0.265 mol), 76.00 g NaSH (59.31 wt%, 0.804 mol), 28.31 g DBDMF (0.080 mol), 106.37 g DCB (0.724 mol), and a total of 299 mL NMP. 87.45 g of a white granular solid was obtained.

[0078] Counterexample 1: (PPS homopolymer) Synthesized according to the procedure of Example 1 (except that DBDMF was not used) using 45.89 g of sodium hydroxide (1.147 mol), 30.45 g of sodium acetate (0.371 mol), 106.95 g of NaSH (58.96 wt%, 1.125 mol), 165.34 g of DCB (1.125 mol), and a total of 418 mL of NMP. 112.60 g of a granular white solid was obtained.

[0079] Counterexample 2: (2.5 mol% DBBP co-PPS) Synthesized according to the procedure of Example 1 (except for using DBBP instead of DBDMF) using 35.41 g sodium hydroxide (0.885 mol), 23.49 g sodium acetate (0.286 mol), 83.89 g NaSH (58.00 wt%, 0.868 mol), 6.77 g DBBP (0.022 mol), 124.39 g DCB (0.846 mol), and a total of 323 mL NMP. 88.05 g of a granular white solid was obtained.

[0080] Counterexample 3: (5 mol% DBBP co-PPS) Synthesized according to the procedure of Counterexample 2 using 35.55 g of sodium hydroxide (0.889 mol), 23.59 g of sodium acetate (0.288 mol), 82.47 g of NaSH (59.23 wt%, 0.871 mol), 13.59 g of DBBP (0.044 mol), 121.68 g of DCB (0.828 mol), and a total of 324 mL of NMP. 94.40 g of a granular white solid was obtained.

[0081] Counterexample 4: (10 mol% DBBP co-PPS) Synthesized according to the procedure of Counterexample 2 using 32.00 g sodium hydroxide (0.800 mol), 21.23 g sodium acetate (0.259 mol), 73.55 g NaSH (59.78 wt%, 0.784 mol), 24.47 g DBBP (0.078 mol), 103.76 g DCB (0.706 mol), and a total of 292 mL NMP. 86.01 g of a granular off-white solid was obtained.

[0082] Counterexample 5: (20 mol% DBBP co-PPS) Synthesized according to the procedure of Counterexample 2 using 33.45 g sodium hydroxide (0.836 mol), 22.19 g sodium acetate (0.271 mol), 78.96 g NaSH (58.21 wt%, 0.820 mol), 51.16 g DBBP (0.164 mol), 96.41 g DCB (0.656 mol), and a total of 305 mL NMP. 95.30 g of a granular off-white solid was obtained.

[0083] Counterexample 6: (40 mol% DBBP co-PPS) Synthesized according to the procedure of Counterexample 2 using 34.90 g sodium hydroxide (0.873 mol), 23.16 g sodium acetate (0.282 mol), 82.39 g NaSH (58.21 wt%, 0.856 mol), 106.77 g DBBP (0.342 mol), 75.45 g DCB (0.513 mol), and a total of 318 mL NMP. 114.0 g of a granular pale yellow solid was obtained.

[0084] Counterexample 7: (10 mol% DBF co-PPS) Synthesized according to the procedure of Example 1 (except for DBF instead of DBDMF) using 32.25 g sodium hydroxide (0.806 mol), 21.40 g sodium acetate (0.261 mol), 74.72 g NaSH (59.31 wt%, 0.791 mol), 25.61 g DBF (0.079 mol), 104.58 g DCB (0.711 mol), and a total of 294 mL of NMP. Polymerization resulted in higher than normal maximum pressure (205 psig compared to the typical 150 psig). The reaction mixture was a brown sludge with a strong odor of thiophenol and other decomposition species. A portion was rinsed according to the procedure, yielding a low molecular weight, light brown powder unsuitable for injection molding.

[0085] Test Method Thermal performance: Tg, T m , T c , and ΔH f was determined using differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans were used in each DSC test: a first heat to 350°C, followed by a first cool to 30°C, followed by a second heat to 350°C. c was measured from the first cooling. g , T m , and ΔH f was measured from the second heat.

[0086] Molecular weight: M w was determined by gel permeation chromatography (GPC) at 210°C using a PL 220 high temperature GPC with a 1-chloronaphthalene mobile phase and polystyrene standards.

[0087] Impact Performance: Notched Izod values ​​were determined according to ASTM D256 using a 0.125 inch bend bar at room temperature.

[0088] Elastic Modulus: Young's modulus was measured according to ASTM D638 using Type V tensile specimens at room temperature with a test speed of 0.05 in / min.

[0089] Thermal and shock performance The test results are shown in Table 1. In Table 1, "E" indicates an example and "CE" indicates a counterexample.

[0090] [Table 1]

[0091] Referring to Table 1, when comparing E3 with CE7, it is surprising that the high M w It has been demonstrated that PAS polymers of this type cannot be synthesized when R1 and R2 (in the X3-Ar2-X4 above) are both hydrogen. CE7, which contains repeat units from dihalofluorene (R1 and R2 are hydrogen), has an M of only 3,400 g / mol. w (Due to the low molecular weight, T g (It was not possible to determine the impact performance and modulus of elasticity of CE7. In particular, the samples were too brittle to be notched, so the impact performance and modulus of elasticity of CE7 could not be measured. Surprisingly, under the same conditions and when R1 and R2 are substituted with methyl groups (E3), the M of 52,200 g / mol was obtained. w A PAS polymer having the following structure was obtained.

[0092] Comparing E1-E3 with CE1-CE5, it is surprising that PAS polymers incorporating dihalofluorene monomers as described herein exhibit increased T relative to similar PAS homopolymers and PAS polymers incorporating DBBP. g For example, comparing E1 to E3 with CE1, it is clear that PAS polymers incorporating repeating units formed from DBDMF exhibit increased T at relatively low concentrations of DBDMF compared to PPS homopolymers. gand impact strength. Similar results were observed when comparing E1-E3 with CE2-CE4, respectively. Furthermore, comparing E1-E3 with CE1-CE4 demonstrates that the PAS polymers incorporating repeat units formed from DBDMF still possess superior modulus.

[0093] The above-described embodiments are intended to be illustrative and not limiting. Additional embodiments are within the concept of the present invention. In addition, while the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the present invention. Any incorporation by reference of the above documents is limited to not incorporating subject matter contrary to the explicit disclosure herein.

Claims

1. The following formulas respectively: [-Ar １ -S-] (1) [-Ar ２ -S-] (2) (In the formula, - -Ar １ -teeth, 【Chemical 1】 and selected from the group of formulas consisting of: - -Ar ２ - is the following formula 【Chemistry 2】 is represented by R and R' are in each case C １ ~C １２ Alkyl group, C ７ ~C ２４ Alkylaryl group, C ７ ~C ２４ Aralkyl group, C ６ ~C ２４ aryl groups, and C ６ ~C １８ aryloxy groups; - T is a bond, -CO-, -SO ２ -, -O-, -C(CH ３ ) ２ -, phenylene, and -CH ２ - selected from the group consisting of; i, at each occurrence, is an independently selected integer from 0 to 4; j and k, at each occurrence, are independently selected integers from 0 to 3; -R １ is hydrogen, fluorine, C １ ~C １２ Alkyl group, C ７ ~C ２４ alkylaryl groups, and C ６ ~C ２４ aryl groups; and -R ２ is fluorine, C １ ~C １２ Alkyl group, C ７ ~C ２４ alkylaryl groups, and C ６ ~C ２４ aryl groups) The repeating unit R ＰＡＳ１ and R ＰＡＳ２ and poly(arylene sulfide) ("PAS") polymers (PASPs), including:

2. -Ar １ - is of the following formula: 【Chemistry 3】 The PAS polymer (PASP) according to claim 1, represented by:

3. -Ar ２ - is of the following formula: 【Chemistry 4】 The PAS polymer (PASP) according to claim 1 or 2, represented by:

4. R １ and R ２ The PAS polymer (PASP) according to any one of claims 1 to 3, wherein is fluorine.

5. R １ and R ２ are independently selected C １ ~C １２ The PAS polymer (PASP) according to any one of claims 1 to 3, which is an alkyl group.

6. -Ar ２ - is 2,7-dibromo-9,9-dimethyl-9H-fluorene; 2,7-dibromo-9,9-dipropyl-9H-fluorene; 2,7-dibromo-9,9-dihexyl-9H-fluorene; 2,7-dibromo-9,9-dioctyl-9H-fluorene; 2,7-dibromo-9,9-didodecyl-9H-fluorene; 2,7-dibromo-9,9-di-(2-ethylhexyl)-9H-fluorene; The PAS polymer (PASP) according to any one of claims 1 to 3, which is a diradical of a dihalofluorene monomer selected from the group consisting of 2,7-dibromo-9,9-diphenyl-9H-fluorene; and 2,7-dibromo-9,9-difluoro-9H-fluorene.

7. Repeating unit (R ＰＡＳ１ ) and (R ＰＡＳ２ ) to the total number of repeating units (R ＰＡＳ２ 7. The PAS polymer (PASP) according to any one of claims 1 to 6, wherein the ratio of the number of aryl groups to the number of alkyl groups is 0.5 mol% to 15 mol%.

8. Repeating unit (R ＰＡＳ１ ) and (R ＰＡＳ２ ) the repeating unit (R ＰＡＳ２ 8. The PAS polymer (PASP) of claim 7, wherein the ratio of the number of

9. T of at least 95°C ｇ The PAS polymer (PASP) according to any one of claims 1 to 8, comprising:

10. T of at least 200°C ｍ The PAS polymer (PASP) according to any one of claims 1 to 9, comprising:

11. A PAS polymer (PASP) according to any one of claims 1 to 10, comprising an impact strength of at least 30 J / g determined according to ASTM D256.

12. A polymer composition (PC) comprising a PAS polymer (PASP) according to any one of claims 1 to 11 and a toughening agent.

13. A polymer composition (PC) comprising a PAS polymer (PASP) according to any one of claims 1 to 11 and glass fibres.

14. An automotive component or an oil and gas component comprising a PAS polymer (PASP) according to any one of claims 1 to 11 or a polymer composition (PC) according to any one of claims 12 or 13.

15. In the reaction mixture, １ -Ar １ -X ２ and a dihaloaromatic compound having the following formula: X ３ -Ar ２ -X ４ A method for producing the PAS polymer (PASP) according to any one of claims 1 to 11, comprising reacting a dihalofluorene monomer having the formula: -X １ ~X ４ are independently selected halogens; the sulfur compounds are selected from the group consisting of thiosulfates, thioureas, thioamides, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and disulfides, and hydrogen sulfide.

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